U.S. patent application number 10/302928 was filed with the patent office on 2003-08-07 for target for transparent electroconductive film, transparent electroconductive material, transparent electroconductive glass and transparent electroconductive film.
This patent application is currently assigned to Idemitsu Kosan Co., Ltd.. Invention is credited to Inoue, Kazuyoshi.
Application Number | 20030148871 10/302928 |
Document ID | / |
Family ID | 27454217 |
Filed Date | 2003-08-07 |
United States Patent
Application |
20030148871 |
Kind Code |
A1 |
Inoue, Kazuyoshi |
August 7, 2003 |
Target for transparent electroconductive film, transparent
electroconductive material, transparent electroconductive glass and
transparent electroconductive film
Abstract
The invention includes sintered products for transparent
electroconductive films, which are formed into films in a stable
and efficient manner through sputtering or the like, sputtering
targets of the sintered products, and transparent electroconductive
glass and films formed from the targets. The transparent
electroconductive glass and films have good transparency, good
electroconductivity and good workability into electrodes, and are
therefore favorable to transparent electrodes in organic
electroluminescent devices as realizing good hole injection
efficiency therein. The sintered products contain constituent
components of indium oxide, tin oxide and zinc oxide in specific
atomic ratios of the metal atoms, and optionally contain specific
metal oxides of ruthenium oxide, molybdenum oxide, vanadium oxide,
etc.
Inventors: |
Inoue, Kazuyoshi; (Tokyo,
JP) |
Correspondence
Address: |
OBLON, SPIVAK, MCCLELLAND, MAIER & NEUSTADT, P.C.
1940 DUKE STREET
ALEXANDRIA
VA
22314
US
|
Assignee: |
Idemitsu Kosan Co., Ltd.
1-1, Marunouchi 3-chome, Chiyoda-ku
Tokyo
JP
|
Family ID: |
27454217 |
Appl. No.: |
10/302928 |
Filed: |
November 25, 2002 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
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10302928 |
Nov 25, 2002 |
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09529416 |
May 1, 2000 |
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09529416 |
May 1, 2000 |
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PCT/JP99/04453 |
Aug 19, 1999 |
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Current U.S.
Class: |
501/134 ;
428/432 |
Current CPC
Class: |
C04B 2235/3289 20130101;
C23C 14/086 20130101; C04B 2235/3286 20130101; C04B 2235/9653
20130101; C04B 2235/77 20130101; C04B 2235/3251 20130101; C04B
2235/767 20130101; C04B 2235/3256 20130101; C03C 2217/23 20130101;
C04B 2235/763 20130101; C04B 2235/3239 20130101; C04B 2235/96
20130101; C08J 2369/00 20130101; C03C 17/2453 20130101; C04B 35/453
20130101; C23C 14/3414 20130101; C03C 2217/231 20130101; C08J 7/044
20200101; C04B 2235/3284 20130101; C04B 2235/3293 20130101; H01L
51/5206 20130101; C03C 2218/154 20130101; G02F 1/13439 20130101;
C04B 2235/80 20130101; C04B 35/457 20130101; C04B 35/01 20130101;
C04B 2235/3262 20130101; H01L 31/022466 20130101; C08J 7/0423
20200101 |
Class at
Publication: |
501/134 ;
428/432 |
International
Class: |
B32B 017/06; C04B
035/453; C04B 035/457 |
Foreign Application Data
Date |
Code |
Application Number |
Aug 31, 1998 |
JP |
10-245322 |
Sep 4, 1998 |
JP |
10-251200 |
Jan 12, 1999 |
JP |
11-005046 |
Mar 5, 1999 |
JP |
11-058384 |
Claims
1. A sintered product that comprises constituent components of
indium oxide, tin oxide and zinc oxide in the following atomic
ratios: In/(In+Sn+Zn)=0.50 to 0.75, Sn/(In+Sn+Zn)=0.20 to 0.45,
Zn/(In+Sn+Zn)=0.03 to 0.30, and contains a hexagonal layer compound
of In.sub.2O.sub.3.(ZnO)m with m indicating an integer of from 2 to
20, and a spinel-structured compound of Zn.sub.2SnO.sub.4.
2. The sintered product as claimed in claim 1, which has a specific
resistance of smaller than 2 m.OMEGA..multidot.cm.
3. A sintered product that comprises constituent components of
indium oxide, tin oxide and zinc oxide in the following atomic
ratios: In/(In+Sn+Zn)=0.50 to 0.75, Sn/(In+Sn+Zn)=0.20 to 0.45,
Zn/(In+Sn+Zn)=0.03 to 0.30, and from 0.5 to 10 atomic %, relative
to the total of all metal atoms therein, of an oxide of a positive
tetra-valent or higher poly-valent metal, and contains a hexagonal
layer compound of In.sub.2O.sub.3.(ZnO)m with m indicating an
integer of from 2 to 20, and a spinel-structured compound of
Zn.sub.2SnO.sub.4.
4. The sintered product as claimed in claim 3, in which the oxide
of a positive tetra-valent or higher poly-valent metal is ruthenium
oxide, molybdenum oxide or vanadium oxide.
5. A sputtering target for transparent electroconductive films,
which comprises the sintered product of any of claims 1 to 4.
6. An electron-beaming target for transparent electroconductive
films, which comprises the sintered product of any of claims 1 to
4.
7. An ion-plating target for transparent electroconductive films,
which comprises the sintered product of any of claims 1 to 4.
8. Transparent electroconductive glass prepared by coating the
surface of glass with an amorphous transparent electroconductive
film that comprises constituent components of indium oxide, tin
oxide and zinc oxide in the following atomic ratios:
In/(In+Sn+Zn)=0.50 to 0.75, Sn/(In+Sn+Zn)=0.20 to 0.45,
Zn/(In+Sn+Zn)=0.03 to 0.30, and contains from 0.5 to 10 atomic %,
relative to the total of all metal atoms therein, of an oxide of a
positive tetra-valent or higher poly-valent metal.
9. The transparent electroconductive glass as claimed in claim 8,
in which the oxide of a positive tetra-valent or higher poly-valent
metal is ruthenium oxide, molybdenum oxide or vanadium oxide.
10. The transparent electroconductive glass as claimed in claim 8
or 9, which has a light transmittance of at least 75% and a
specific resistance of at most 5 m.OMEGA..multidot.cm, and in which
the transparent electroconductive film has a work function of at
least 5.45.
11. A transparent electroconductive film prepared by coating the
surface of a transparent resin film with an amorphous transparent
electroconductive layer that comprises constituent components of
indium oxide, tin oxide and zinc oxide in the following atomic
ratios: In/(In+Sn+Zn)=0.50 to 0.75, Sn/(In+Sn+Zn)=0.20 to 0.45,
Zn/(In+Sn+Zn)=0.03 to 0.30, and contains from 0.5 to 10 atomic %,
relative to the total of all metal atoms therein, of an oxide of a
positive tetra-valent or higher poly-valent metal.
12. The transparent electroconductive film as claimed in claim 11,
in which the oxide of a positive tetra-valent or higher poly-valent
metal is ruthenium oxide, molybdenum oxide or vanadium oxide.
13. The transparent electroconductive film as claimed in claim 11
or 12, which has a light transmittance of at least 75% and a
specific resistance of at most 5 m.OMEGA..multidot.cm, and in which
the transparent electroconductive layer has a work function of at
least 5.45.
14. A sintered product of a composition that comprises indium
oxide, or indium oxide and zinc oxide and/or tin oxide in the
following atomic ratios: In/(In+Zn+Sn)=0.80 to 1.00,
Zn/(In+Zn+Sn)=0.00 to 0.20, Sn/(In+Zn+Sn)=0.00 to 0.20, and
contains from 0.5 to 10 atomic %, relative to the total of all
metal atoms therein, of a metal oxide selected from ruthenium
oxide, molybdenum oxide and vanadium oxide.
15. A sintered product of a composition that comprises indium oxide
and zinc oxide, or tin oxide in addition to the former two oxides
in the following atomic ratios: In/(In+Zn+Sn)=0.80 to 1.00,
Zn/(In+Zn+Sn)=0.05 to 0.20, Sn/(In+Zn+Sn)=0.00 to 0.20, and
contains from 0.5 to 10 atomic %, relative to the total of all
metal atoms therein, of a metal oxide selected from ruthenium
oxide, molybdenum oxide and vanadium oxide.
16. A sintered product of a composition that comprises indium
oxide, zinc oxide and tin oxide in the following atomic ratios:
In/(In+Zn+Sn)=0.80 to 1.00, Zn/(In+Zn+Sn)=0.05 to 0.20,
Sn/(In+Zn+Sn)=0.02 to 0.20, and contains from 0.5 to 10 atomic %,
relative to the total of all metal atoms therein, of a metal oxide
selected from ruthenium oxide, molybdenum oxide and vanadium
oxide.
17. A sputtering target comprising the sintered product of any of
claims 13 to 16.
18. An electron-beaming target comprising the sintered product of
any of claims 13 to 16.
19. An ion-plating target comprising the sintered product of any of
claims 13 to 16.
20. Transparent electroconductive glass prepared by coating the
surface of glass with a transparent electroconductive film of a
composition that comprises indium oxide, zinc oxide and tin oxide
in the following atomic ratios: In/(In+Zn+Sn)=0.80 to 1.00,
Zn/(In+Zn+Sn)=0.00 to 0.20, Sn/(In+Zn+Sn)=0.00 to 0.20, and
contains from 0.5 to 10 atomic %, relative to the total of all
metal atoms therein, of a metal oxide selected from ruthenium
oxide, molybdenum oxide and vanadium oxide.
21. The transparent electroconductive glass as claimed in claim 20,
which has a light transmittance of at least 75% and a specific
resistance of at most 5 m.OMEGA..multidot.cm, and in which the
transparent electroconductive film has a work function of at least
5.45 electron volts.
22. A transparent electroconductive film prepared by coating the
surface of a transparent resin film with a transparent
electroconductive layer that comprises indium oxide, zinc oxide and
tin oxide in the following atomic ratios: In/(In+Zn+Sn)=0.80 to
1.00, Sn/(In+Zn+Sn)=0.00 to 0.20, Zn/(In+Zn+Sn)=0.00 to 0.20, and
contains from 0.5 to 10 atomic %, relative to the total of all
metal atoms therein, of a metal oxide selected from ruthenium
oxide, molybdenum oxide and vanadium oxide.
23. The transparent electroconductive film as claimed in claim 22,
which has a light transmittance of at least 75% and a specific
resistance of at most 5 m.OMEGA..multidot.cm, and in which the
transparent electroconductive layer has a work function of at least
5.45 electron volts.
24. A transparent electroconductive material of a composition that
comprises one or more metal oxides selected from indium oxide, zinc
oxide and tin oxide and contains from 0.5 to 20 atomic %, relative
to the total of all metal atoms therein, of one or more metal
oxides selected from iridium oxide, rhenium oxide and palladium
oxide.
25. A transparent electroconductive material of a composition that
comprises metal oxide(s) of indium oxide, zinc oxide and tin oxide
in the following atomic ratios: In/(In+Zn+Sn)=0.00 to 1.00,
Zn/(In+Zn+Sn)=0.00 to 0.25, Sn/(In+Zn+Sn)=0.00 to 1.00, and
contains from 0.5 to 20 atomic %, relative to the total of all
metal atoms therein, of one or more metal oxides selected from
iridium oxide, rhenium oxide and palladium oxide.
26. A transparent electroconductive material of a composition that
comprises metal oxides of indium oxide, zinc oxide and tin oxide in
the following atomic ratios: In/(In+Zn+Sn)=0.50 to 1.00,
Zn/(In+Zn+Sn)=0.05 to 0.25, Sn/(In+Zn+Sn)=0.00 to 0.50, and
contains from 0.5 to 20 atomic %, relative to the total of all
metal atoms therein, of one or more metal oxides selected from
iridium oxide, rhenium oxide and palladium oxide.
27. A transparent electroconductive material of a composition that
comprises metal oxides of indium oxide, zinc oxide and tin oxide in
the following atomic ratios: In/(In+Zn+Sn)=0.75 to 0.95,
Zn/(In+Zn+Sn)=0.05 to 0.20, Sn/(In+Zn+Sn)=0.00 to 0.20, and
contains from 0.5 to 20 atomic %, relative to the total of all
metal atoms therein, of one or more metal oxides selected from
iridium oxide, rhenium oxide and palladium oxide.
28. A sintered product prepared by sintering the composition of any
of claims 24 to 27.
29. A sputtering target comprising the sintered product of claim
28.
30. Transparent electroconductive glass prepared by coating the
surface of glass with a transparent electroconductive film of a
composition that comprises one or more metal oxides selected from
indium oxide, zinc oxide and tin oxide and contains from 0.5 to 20
atomic %, relative to the total of all metal atoms therein, of one
or more metal oxides selected from iridium oxide, rhenium oxide and
palladium oxide.
31. The transparent electroconductive glass as claimed in claim 30,
which has a light transmittance of at least 70% and in which the
transparent electroconductive film has a work function of at least
5.4 electron volts.
32. A transparent electroconductive film prepared by coating the
surface of a transparent resin film with a transparent
electroconductive layer that comprises one or more metal oxides
selected from indium oxide, zinc oxide and tin oxide and contains
from 0.5 to 20 atomic %, relative to the total of all metal atoms
therein, of one or more metal oxides selected from iridium oxide,
rhenium oxide and palladium oxide.
33. The transparent electroconductive film as claimed in claim 32,
which has a light transmittance of at least 70% and in which the
transparent electroconductive layer has a work function of at least
5.4 electron volts.
34. A transparent electroconductive material of a composition that
comprises metal oxide(s) of tin oxide, indium oxide and zinc oxide
in the following atomic ratios: Sn/(Sn+In+Zn)=0.55 to 1.00,
In/(Sn+In+Zn)=0.00 to 0.45, Zn/(Sn+In+Zn)=0.00 to 0.25, and
contains from 0.5 to 10 atomic %, relative to the total of all
metal atoms therein, of one or more metal oxides selected from
vanadium oxide, molybdenum oxide and ruthenium oxide.
35. The transparent electroconductive material as claimed in claim
34, in which tin oxide, indium oxide and zinc oxide are in the
following atomic ratios: Sn/(Sn+In+Zn)=0.55 to 0.95,
In/(Sn+In+Zn)=0.00 to 0.40, Zn/(Sn+In+Zn)=0.05 to 0.25.
36. The transparent electroconductive material as claimed in claim
34, in which tin oxide, indium oxide and zinc oxide are in the
following atomic ratios: Sn/(Sn+In+Zn)=0.55 to 0.95,
In/(Sn+In+Zn)=0.00 to 0.40, Zn/(Sn+In+Zn)=0.05 to 0.20.
37. The transparent electroconductive material as claimed in claim
34, in which tin oxide, indium oxide and zinc oxide are in the
following atomic ratios: Sn/(Sn+In+Zn)=0.60 to 0.95,
In/(Sn+In+Zn)=0.00 to 0.35, Zn/(Sn+In+Zn)=0.05 to 0.20.
38. A sintered product prepared by sintering the composition of any
of claims 34 to 37 at a temperature of not lower than 1200.degree.
C.
39. A sputtering target comprising the sintered product of claim
38, which has a specific resistance of at most 10
m.OMEGA..multidot.cm.
40. Transparent electroconductive glass prepared by forming, on the
surface of a glass substrate, a transparent electroconductive film
of a composition that comprises metal oxide(s) of tin oxide, indium
oxide and zinc oxide in the following atomic ratios:
Sn/(Sn+In+Zn)=0.55 to 1.00, In/(Sn+In+Zn)=0.00 to 0.45,
Zn/(Sn+In+Zn)=0.00 to 0.25, and contains from 0.5 to 10 atomic %,
relative to the total of all metal atoms therein, of one or more
metal oxides selected from vanadium oxide, molybdenum oxide and
ruthenium oxide.
41. The transparent electroconductive glass as claimed in claim 40,
in which the transparent electroconductive film has a light
transmittance of at least 70% and a work function of at least 5.4
electron volts.
42. A transparent electroconductive film prepared by forming, on
the surface of a transparent resin film, a transparent
electroconductive layer of a composition that comprises metal
oxide(s) of tin oxide, indium oxide and zinc oxide in the following
atomic ratios: Sn/(Sn+In+Zn)=0.55 to 1.00, In/(Sn+In+Zn)=0.00 to
0.45, Zn/(Sn+In+Zn)=0.00 to 0.25, and contains from 0.5 to 10
atomic %, relative to the total of all metal atoms therein, of one
or more metal oxides selected from vanadium oxide, molybdenum oxide
and ruthenium oxide.
43. The transparent electroconductive film as claimed in claim 42,
in which the transparent electroconductive layer has a light
transmittance of at least 70% and a work function of at least 5.4
electron volts.
Description
TECHNICAL FIELD
[0001] The present invention relates to sintered metal oxides of
great use as blanks for transparent electroconductive films for
display devices and others, to targets of the sintered products for
forming transparent electroconductive films, to transparent
electroconductive materials, and to transparent electroconductive
glass and films formed from the targets.
BACKGROUND ART
[0002] Recently, various display devices such as liquid-crystal
displays, electroluminescent displays, field emission displays and
others have been introduced into office appliances and also control
systems in factories. These devices all have a sandwich structure
with a display member put between transparent electroconductive
films.
[0003] For the transparent electroconductive films, much used is
indium oxide-tin oxide (hereinafter referred to as ITO) to give ITO
films. The ITO films are highly transparent and have low electric
resistance, and, in addition, they are well etched and their
adhesiveness to substrates is good. As having such good properties,
the ITO films are widely used in the art. In general, the ITO films
are formed in various methods of sputtering, ion-plating, vapor
deposition, etc.
[0004] Though having such good properties, however, there still
remain some problems to be solved with the ITO films when they are
used, for example, as transparent electrodes for liquid-crystal
display devices. The problems with the ITO films include their
surface accuracy, the tapering processability of electrodes made of
them, and their workability into electrodes with junctions or
contact points.
[0005] Specifically, ITO itself is a crystalline metal oxide, and
its crystal grains grow in the step of forming it into films. The
growing crystal grains deposit on the surface of the ITO film,
thereby lowering the surface accuracy of the film. In the step of
etching the ITO film for forming an electrode, the intergranular
boundaries in the film are first etched, and the etched surface of
the electrode shall be roughened. Therefore, it is difficult to
etch the ITO film with accuracy. Further, in the step of tapering
the ITO film electrode, the intergranular boundaries in the film
are also first etched, and the ITO grains will often remain in the
etched area. In that condition, the ITO film electrode could not be
well insulated from the counter electrode, thereby often causing
display failure.
[0006] To solve the problem, a transparent electroconductive
material comprising indium oxide and zinc oxide was proposed, for
example, in Japanese Patent Laid-Open No. 234565/1994. Its
workability into electrodes was improved without its transparency
and electroconductivity being not sacrificed. However, the indium
oxide-zinc oxide material has a bulk resistance of from 2 to 5
m.OMEGA..multidot.cm, and the electric power to be applied thereto
for forming it into films is limited. Therefore, the problem with
the material is that the productivity in forming it into films is
low.
[0007] In an organic electroluminescent device having a film
electrode of ITO, holes must be transferred from the ITO film
electrode into the light emission layer or into the hole
transporting layer. For this, it is desirable that the work
function of the electrode material and that of the organic compound
for the light emission layer or the hole transporting layer are
nearly on the same level and that the energy gap between the anode
and the hole transporting layer is as small as possible. To reduce
the energy gap, the difference between the work function of the
anode material and the ionization potential of the organic compound
for the hole transporting layer must be reduced. Various organic
compounds have been proposed for hole-transporting substances
usable for forming the hole transporting layer. Of those, aromatic
amine compounds, especially triphenylamine derivatives have been
known to have good capabilities. Triphenylamine, one of
triphenylamine derivatives, has an ionization potential of from 5.5
to 5.6 electron volts. On the other hand, for transparent
electroconductive films, well known is indium * oxide-tin oxide
(hereinafter referred to as ITO) having high transparency and low
electric resistance. The work function of ITO is 4.6 electron
volts. Accordingly, there shall be a relatively large energy gap
between the anode and the electron transportation layer both of
such ordinary materials.
[0008] In that situation, proposed was an organic, light-emitting
thin-film device having an organic compound layer between an anode
and a cathode, for example, in Japanese Patent Laid-Open No.
63771/1997. In this, the anode is of a thin film of a metal oxide
of which the work function is larger than that of ITO. However, the
thin-film anode of such a metal oxide has a light transmittance of
10% when the metal oxide is ruthenium oxide, and 20% when it is
vanadium oxide. To increase the light transmittance, proposed was a
two-layered structure composed of an ITO film and an ultra-thin
film of the metal oxide, the ultra-thin film having a thickness of
not larger than 300 angstroms. Even in this case, however, the
light transmittance of the two-layered structure is still 40 to 60%
or so. Therefore, the two-layered structure is still problematic in
that its transparency is not satisfactory for transparent
electrodes for display devices.
DISCLOSURE OF THE INVENTION
[0009] The present invention is to provide sintered metal oxides
capable of being formed into films in a stable and efficient manner
through sputtering or the like, targets of the sintered products,
and transparent electroconductive glass and films formed from the
targets. The transparent electroconductive glass and films have
good transparency, good electroconductivity and good workability
into electrodes, and when they are formed into transparent
electrodes and used in organic electroluminescent devices, the
difference between their work function and the ionization potential
of the hole-transporting substances in the devices is small and
therefore the transparent electrodes do not lower the light
emission efficiency of the devices.
[0010] Having assiduously studied so as to solve the problems noted
above, we, the present inventors have found that using sintered
products of compounds, which comprise indium oxide, tin oxide and
zinc oxide in a specific ratio, as transparent electroconductive
materials solves the problems. On the basis of this finding, we
have completed the present invention.
[0011] Specifically, the invention includes first to fourth
aspects, which are summarized as follows:
[0012] [I] First Aspect of the Invention:
[0013] [1] A sintered product that comprises constituent components
of indium oxide, tin oxide and zinc oxide in the following atomic
ratios:
In/(In+Sn+Zn)=0.50 to 0.75,
Sn/(In+Sn+Zn)=0.20 to 0.45,
Zn/(In+Sn+Zn)=0.03 to 0.30,
[0014] and contains a hexagonal layer compound of
In.sub.2O.sub.3.(ZnO)m with m indicating an integer of from 2 to
20, and a spinel-structured compound of Zn.sub.2SnO.sub.4.
[0015] [2] The sintered product of above [1], which has a specific
resistance of smaller than 2 m.OMEGA..multidot.cm.
[0016] [3] A sintered product that comprises constituent components
of indium oxide, tin oxide and zinc oxide in the following atomic
ratios:
In/(In+Sn+Zn)=0.50 to 0.75,
Sn/(In+Sn+Zn)=0.20 to 0.45,
Zn/(In+Sn+Zn)=0.03 to 0.30,
[0017] and from 0.5 to 10 atomic %, relative to the total of all
metal atoms therein, of an oxide of a positive tetra-valent or
higher poly-valent metal, and contains a hexagonal layer compound
of In.sub.2O.sub.3.(ZnO)m with m indicating an integer of from 2 to
20, and a spinel-structured compound of Zn.sub.2SnO.sub.4.
[0018] [4] The sintered product of above [3], in which the oxide of
a positive tetra-valent or higher poly-valent metal is ruthenium
oxide, molybdenum oxide or vanadium oxide.
[0019] [5] A sputtering target for transparent electroconductive
films, which comprises the sintered product of any of above [1] to
[4].
[0020] [6] An electron-beaming target for transparent
electroconductive films, which comprises the sintered product of
any of above [1] to [4].
[0021] [7] An ion-plating target for transparent electroconductive
films, which comprises the sintered product of any of above [1] to
[4].
[0022] [8] Transparent electroconductive glass prepared by coating
the surface of glass with an amorphous transparent
electroconductive film that comprises constituent components of
indium oxide, tin oxide and zinc oxide in the following atomic
ratios:
In/(In+Sn+Zn)=0.50 to 0.75,
Sn/(In+Sn+Zn)=0.20 to 0.45,
Zn/(In+Sn+Zn)=0.03 to 0.30,
[0023] and contains from 0.5 to 10 atomic %, relative to the total
of all metal atoms therein, of an oxide of a positive tetra-valent
or higher poly-valent metal.
[0024] [9] The transparent electroconductive glass of above [8], in
which the oxide of a positive tetra-valent or higher poly-valent
metal is ruthenium oxide, molybdenum oxide or vanadium oxide.
[0025] [10] The transparent electroconductive glass of above [8] or
[9], which has a light transmittance of at least 75% and a specific
resistance of at most 5 m.OMEGA..multidot.cm, and in which the
transparent electroconductive film has a work function of at least
5.45.
[0026] [11] A transparent electroconductive film prepared by
coating the surface of a transparent resin film with an amorphous
transparent electroconductive layer that comprises constituent
components of indium oxide, tin oxide and zinc oxide in the
following atomic ratios:
In/(In+Sn+Zn)=0.50 to 0.75,
Sn/(In+Sn+Zn)=0.20 to 0.45,
Zn/(In+Sn+Zn)=0.03 to 0.30,
[0027] and contains from 0.5 to 10 atomic %, relative to the total
of all metal atoms therein, of an oxide of a positive tetra-valent
or higher poly-valent metal.
[0028] [12] The transparent electroconductive film of above [11],
in which the oxide of a positive tetra-valent or higher poly-valent
metal is ruthenium oxide, molybdenum oxide or vanadium oxide.
[0029] [13] The transparent electroconductive film of above [11] or
[12], which has a light transmittance of at least 75% and a
specific resistance of at most 5 m.OMEGA..multidot.cm, and in which
the transparent electroconductive layer has a work function of at
least 5.45.
[0030] [II] Second Aspect of the Invention:
[0031] [1] A sintered product of a composition that comprises
indium oxide, or indium oxide and zinc oxide and/or tin oxide in
the following atomic ratios:
In/(In+Zn+Sn)=0.80 to 1.00,
Zn/(In+Zn+Sn)=0.00 to 0.20,
Sn/(In+Zn+Sn)=0.00 to 0.20,
[0032] and contains from 0.5 to 10 atomic %, relative to the total
of all metal atoms therein, of a metal oxide selected from
ruthenium oxide, molybdenum oxide and vanadium oxide.
[0033] [2] A sintered product of a composition that comprises
indium oxide and zinc oxide, or tin oxide in addition to the former
two oxides in the following atomic ratios:
In/(In+Zn+Sn)=0.80 to 1.00,
Zn/(In+Zn+Sn)=0.05 to 0.20,
Sn/(In+Zn+Sn)=0.00 to 0.20,
[0034] and contains from 0.5 to 10 atomic %, relative to the total
of all metal atoms therein, of a metal oxide selected from
ruthenium oxide, molybdenum oxide and vanadium oxide.
[0035] [3] A sintered product of a composition that comprises
indium oxide, zinc oxide and tin oxide in the following atomic
ratios:
In/(In+Zn+Sn)=0.80 to 1.00,
Zn/(In+Zn+Sn)=0.05 to 0.20,
Sn/(In+Zn+Sn)=0.02 to 0.20,
[0036] and contains from 0.5 to 10 atomic %, relative to the total
of all metal atoms therein, of a metal oxide selected from
ruthenium oxide, molybdenum oxide and vanadium oxide.
[0037] [4] A sputtering target comprising the sintered product of
any of above [1] to [3].
[0038] [5] An electron-beaming target comprising the sintered
product of any of above [1] to [3].
[0039] [6] An ion-plating target comprising the sintered product of
any of above [1] to [3].
[0040] [7] Transparent electroconductive glass prepared by coating
the surface of glass with a transparent electroconductive film of a
composition that comprises indium oxide, zinc oxide and tin oxide
in the following atomic ratios:
In/(In+Zn+Sn)=0.80 to 1.00,
Zn/(In+Zn+Sn)=0.00 to 0.20,
Sn/(In+Zn+Sn)=0.00 to 0.20,
[0041] and contains from 0.5 to 10 atomic %, relative to the total
of all metal atoms therein, of a metal oxide selected from
ruthenium oxide, molybdenum oxide and vanadium oxide.
[0042] [8] The transparent electroconductive glass of above [7],
which has a light transmittance of at least 75% and a specific
resistance of at most 5 m.OMEGA..multidot.cm, and in which the
transparent electroconductive film has a work function of at least
5.45 electron volts.
[0043] [9] A transparent electroconductive film prepared by coating
the surface of a transparent resin film with a transparent
electroconductive layer that comprises indium oxide, zinc oxide and
tin oxide in the following atomic ratios:
In/(In+Zn+Sn)=0.80 to 1.00,
Zn/(In+Zn+Sn)=0.00 to 0.20,
Sn/(In+Zn+Sn)=0.00 to 0.20,
[0044] and contains from 0.5 to 10 atomic %, relative to the total
of all metal atoms therein, of a metal oxide selected from
ruthenium oxide, molybdenum oxide and vanadium oxide.
[0045] [10] The transparent electroconductive film of above [9],
which has a light transmittance of at least 75% and a specific
resistance of at most 5 m.OMEGA..multidot.cm, and in which the
transparent electroconductive layer has a work function of at least
5.45 electron volts.
[0046] [III] Third Aspect of the Invention:
[0047] [1] A transparent electroconductive material of a
composition that comprises one or more metal oxides selected from
indium oxide, zinc oxide and tin oxide and contains from 0.5 to 20
atomic %, relative to the total of all metal atoms therein, of one
or more metal oxides selected from iridium oxide, rhenium oxide and
palladium oxide.
[0048] [2] A transparent electroconductive material of a
composition that comprises metal oxide(s) of indium oxide, zinc
oxide and tin oxide in the following atomic ratios:
In/(In+Zn+Sn)=0.00 to 1.00,
Zn/(In+Zn+Sn)=0.00 to 0.25,
Sn/(In+Zn+Sn)=0.00 to 1.00,
[0049] and contains from 0.5 to 20 atomic %, relative to the total
of all metal atoms therein, of one or more metal oxides selected
from iridium oxide, rhenium oxide and palladium oxide.
[0050] [3] A transparent electroconductive material of a
composition that comprises metal oxides of indium oxide, zinc oxide
and tin oxide in the following atomic ratios:
In/(In+Zn+Sn)=0.50 to 1.00,
Zn/(In+Zn+Sn)=0.05 to 0.25,
Sn/(In+Zn+Sn)=0.00 to 0.50,
[0051] and contains from 0.5 to 20 atomic %, relative to the total
of all metal atoms therein, of one or more metal oxides selected
from iridium oxide, rhenium oxide and palladium oxide.
[0052] [4] A transparent electroconductive material of a
composition that comprises metal oxides of indium oxide, zinc oxide
and tin oxide in the following atomic ratios:
In/(In+Zn+Sn)=0.75 to 0.95,
Zn/(In+Zn+Sn)=0.05 to 0.20,
Sn/(In+Zn+Sn)=0.00 to 0.20,
[0053] and contains from 0.5 to 20 atomic %, relative to the total
of all metal atoms therein, of one or more metal oxides selected
from iridium oxide, rhenium oxide and palladium oxide.
[0054] [5] A sintered product prepared by sintering the composition
of any of above [1] to [4].
[0055] [6] A sputtering target comprising the sintered product of
above [5].
[0056] [7] Transparent electroconductive glass prepared by coating
the surface of glass with a transparent electroconductive film of a
composition that comprises one or more metal oxides selected from
indium oxide, zinc oxide and tin oxide and contains from 0.5 to 20
atomic %, relative to the total of all metal atoms therein, of one
or more metal oxides selected from iridium oxide, rhenium oxide and
palladium oxide.
[0057] [8] The transparent electroconductive glass of above [7],
which has a light transmittance of at least 70% and in which the
transparent electroconductive film has a work function of at least
5.4 electron volts.
[0058] [9] A transparent electroconductive film prepared by coating
the surface of a transparent resin film with a transparent
electroconductive layer that comprises one or more metal oxides
selected from indium oxide, zinc oxide and tin oxide and contains
from 0.5 to 20 atomic %, relative to the total of all metal atoms
therein, of one or more metal oxides selected from iridium oxide,
rhenium oxide and palladium oxide.
[0059] [10] The transparent electroconductive film of above [9],
which has a light transmittance of at least 70% and in which the
transparent electroconductive layer has a work function of at least
5.4 electron volts.
[0060] Fourth Aspect of the Invention [1] A transparent
electroconductive material of a composition that comprises metal
oxide(s) of tin oxide, indium oxide and zinc oxide in the following
atomic ratios:
Sn/(Sn+In+Zn)=0.55 to 1.00,
In/(Sn+In+Zn)=0.00 to 0.45,
Zn/(Sn+In+Zn)=0.00 to 0.25,
[0061] and contains from 0.5 to 10 atomic %, relative to the total
of all metal atoms therein, of one or more metal oxides selected
from vanadium oxide, molybdenum oxide and ruthenium oxide.
[0062] [2] The transparent electroconductive material of above [1],
in which tin oxide, indium oxide and zinc oxide are in the
following atomic ratios:
Sn/(Sn+In+Zn)=0.55 to 0.95,
In/(Sn+In+Zn)=0.00 to 0.40,
Zn/(Sn+In+Zn)=0.05 to 0.25.
[0063] [3] The transparent electroconductive material of above [1],
in which tin oxide, indium oxide and zinc oxide are in the
following atomic ratios:
Sn/(Sn+In+Zn)=0.55 to 0.95,
In/(Sn+In+Zn)=0.00 to 0.40,
Zn/(Sn+In+Zn)=0.05 to 0.20.
[0064] [4] The transparent electroconductive material of above [1],
in which tin oxide, indium oxide and zinc oxide are in the
following atomic ratios:
Sn/(Sn+In+Zn)=0.60 to 0.95,
In/(Sn+In+Zn)=0.00 to 0.35,
Zn/(Sn+In+Zn)=0.05 to 0.20.
[0065] [5] A sintered product prepared by sintering the composition
of any of above [1] to [4] at a temperature of not lower than
1200.degree. C.
[0066] [6] A sputtering target comprising the sintered product of
above [5], which has a specific resistance of at most 10
m.OMEGA..multidot.cm.
[0067] [7] Transparent electroconductive glass prepared by forming,
on the surface of a glass substrate, a transparent
electroconductive film of a composition that comprises metal
oxide(s) of tin oxide, indium oxide and zinc oxide in the following
atomic ratios:
Sn/(Sn+In+Zn)=0.55 to 1.00,
In/(Sn+In+Zn)=0.00 to 0.45,
Zn/(Sn+In+Zn)=0.00 to 0.25,
[0068] and contains from 0.5 to 10 atomic %, relative to the total
of all metal atoms therein, of one or more metal oxides selected
from vanadium oxide, molybdenum oxide and ruthenium oxide.
[0069] [8] The transparent electroconductive glass of above [7], in
which the transparent electroconductive film has a light
transmittance of at least 70% and a work function of at least 5.4
electron volts.
[0070] [9] A transparent electroconductive film prepared by
forming, on the surface of a transparent resin film, a transparent
electroconductive layer of a composition that comprises metal
oxide(s) of tin oxide, indium oxide and zinc oxide in the following
atomic ratios:
Sn/(Sn+In+Zn)=0.55 to 1.00,
In/(Sn+In+Zn)=0.00 to 0.45,
Zn/(Sn+In+Zn)=0.00 to 0.25,
[0071] and contains from 0.5 to 10 atomic %, relative to the total
of all metal atoms therein, of one or more metal oxides selected
from vanadium oxide, molybdenum oxide and ruthenium oxide.
[0072] [10] The transparent electroconductive film of above [9], in
which the transparent electroconductive layer has a light
transmittance of at least 70% and a work function of at least 5.4
electron volts.
BEST MODES OF CARRYING OUT THE INVENTION
[0073] Embodiments of the invention are described below.
[0074] First Aspect of the Invention
[0075] The sintered product of the invention is a transparent
electroconductive material for forming transparent
electroconductive films, and its basic constituent components are
indium oxide, tin oxide and zinc oxide.
[0076] In this, the constituent components are in the following
atomic ratios:
In/(In+Sn+Zn)=0.50 to 0.75,
Sn/(In+Sn+Zn)=0.20 to 0.45,
Zn/(In+Sn+Zn)=0.03 to 0.30,
[0077] preferably,
In/(In+Sn+Zn)=0.60 to 0.75,
Sn/(In+Sn+Zn)=0.20 to 0.35,
Zn/(In+Sn+Zn)=0.05 to 0.20,
[0078] more preferably,
In/(In+Sn+Zn)=0.60 to 0.70,
Sn/(In+Sn+Zn)=0.25 to 0.35,
Zn/(In+Sn+Zn)=0.05 to 0.15.
[0079] In the invention, the composition of the constituent
components, indium oxide, tin oxide and zinc oxide is defined as
above. This is because when a mixture of indium oxide and zinc
oxide is baked at low temperatures, the electroconductivity of the
resulting sintered product is low. In the invention, the reduction
in the electroconductivity of the sintered product is prevented.
When the mixture of indium oxide and zinc oxide is baked at high
temperatures, the resulting sintered product could be a hexagonal
layer compound with increased electroconductivity. In the mixture,
however, it is difficult to convert zinc oxide entirely into a
hexagonal layer compound, and the increase in the
electroconductivity of the sintered product is limited.
Accordingly, in the invention, zinc oxide that could not be
converted into a hexagonal layer compound is reacted with tin oxide
to form a spinel-structured compound, whereby the
electroconductivity of the sintered product of the composition is
increased and the sputtering stability of targets of the sintered
product is ensured.
[0080] Regarding the blend ratio of these components, if the atomic
ratio of indium oxide is smaller than 0.50, the surface resistance
of the transparent electroconductive film to be obtained herein
will be high and the heat resistance thereof will be low; but if
larger than 0.75, the transparent electroconductive film will
crystallize to lower its transparency. If the atomic ratio of tin
oxide is smaller than 0.20, forming the spinel-structured compound
of zinc oxide and tin oxide will be incomplete; but if larger than
0.45, the surface resistance of the transparent electroconductive
film will be high. If the atomic ratio of zinc oxide is smaller
than 0.03, the transparent electroconductive film will readily
crystallize; but if larger than 0.30, the heat resistance of the
film will be low.
[0081] The sintered product comprises the constituent metal oxides
of which the composition falls within the defined range as above,
and contains a hexagonal layer compound of In.sub.2O.sub.3.(ZnO)m
with m indicating an integer of from 2 to 20, and a
spinel-structured compound of Zn.sub.2SnO.sub.4.
[0082] The sintered product of the invention that comprises the
constituent components as above has high electroconductivity as so
mentioned hereinabove, and its specific resistance is lower than 2
m.OMEGA..multidot.cm. Accordingly, when a target of the sintered
product is sputtered to form a film in a sputtering device, the
sputtering stability is good and the productivity in producing the
film product is good.
[0083] The sintered product that comprises the constituent
components, indium oxide, tin oxide and zinc oxide, and
additionally contains from 0.5 to 10 atomic %, relative to the
total of all metal atoms therein, an oxide of a positive
tetra-valent or higher poly-valent metal, especially preferably
ruthenium oxide, molybdenum oxide or vanadium oxide has a work
function falling between 5.45 and 5.70 electron volts, and its work
function is nearly on the same level as the average work function,
5.6 electron volts, of organic compounds for light-emitting
substances or hole-transporting substances for organic
electroluminescent devices. Accordingly, transparent
electroconductive films formed by sputtering a target of the
sintered product shall have high hole injection efficiency when
used in organic electroluminescent devices. In the sintered
product, the proportion of the oxide of a positive tetra-valent or
higher poly-valent metal preferably falls between 1 and 5 atomic %
to the total of all metal atoms.
[0084] For producing the sintered product of the invention, for
example, employed is a method comprising uniformly mixing and
grinding powders of starting metal oxides in a mixing and grinding
machine, for example, in a wet ball or bead mill or ultrasonically,
then granulating the resulting mixture, shaping the resulting
granules into bodies of desired form by pressing, and finally
baking them into sintered products. In this, the raw material
powders are preferably mixed and ground as fine as possible, but,
in general, they are mixed and ground to have a mean grain size of
not larger than 1 .mu.m. In the baking step, the shaped bodies are
baked generally at a temperature falling between 1,200 and
1,500.degree. C., but preferably between 1,250 and 1,480.degree.
C., for a period of time generally falling between 10 and 72 hours,
but preferably between 24 and 48 hours. In this, the heating rate
may fall between 1 and 50.degree. C./min.
[0085] In the baking step, the baking temperature is preferably not
lower than 1,250.degree. C. in order that indium oxide and zinc
oxide in the resulting sintered product could form a hexagonal
layer compound of the formula noted above. The baking temperature
shall be at lowest 1,000.degree. C. in order that zinc oxide and
tin oxide could form a spinel-structured compound.
[0086] Where the three-component system of the metal oxides is
combined with an oxide of a positive tetra-valent or higher
poly-valent metal, such as ruthenium oxide, molybdenum oxide or
vanadium oxide in preparing the sintered product of the invention,
a suitable amount of powder of the additional metal oxide such as
ruthenium oxide is added to the powders of the starting,
three-component system metal oxides, and baked in the same manner
as above. Also in this case, baking the shaped bodies is effected
under the condition under which the hexagonal layer compound of
indium oxide and zinc oxide and the spinel-structured compound of
zinc oxide and tin oxide could be formed in the resulting sintered
product.
[0087] [II] Second Aspect of the Invention:
[0088] The sintered product of the invention for forming
transparent electroconductive films is of a composition that
comprises indium oxide, or indium oxide and zinc oxide and/or tin
oxide in the following atomic ratios:
In/(In+Zn+Sn)=0.80 to 1.00,
Zn/(In+Zn+Sn)=0.00 to 0.20,
Sn/(In+Zn+Sn)=0.00 to 0.20,
[0089] and contains from 0.5 to 10 atomic %, relative to the total
of all metal atoms therein, of a metal oxide selected from
ruthenium oxide, molybdenum oxide and vanadium oxide.
[0090] More preferably, the sintered product is of a composition
that comprises indium oxide and zinc oxide, or tin oxide in
addition to the former two oxides in the following atomic
ratios:
In/(In+Zn+Sn)=0.80 to 1.00,
Zn/(In+Zn+Sn)=0.05 to 0.20,
Sn/(In+Zn+Sn)=0.00 to 0.20,
[0091] and contains from 0.5 to 10 atomic %, relative to the total
of all metal atoms therein, of a metal oxide selected from
ruthenium oxide, molybdenum oxide and vanadium oxide.
[0092] Most preferably, the sintered product is of a composition
that comprises indium oxide, zinc oxide and tin oxide in the
following atomic ratios:
In/(In+Zn+Sn)=0.80 to 1.00,
Zn/(In+Zn+Sn)=0.05 to 0.20,
Sn/(In+Zn+Sn)=0.02 to 0.20,
[0093] and contains from 0.5 to 10 atomic %, relative to the total
of all metal atoms therein, of a metal oxide selected from
ruthenium oxide, molybdenum oxide and vanadium oxide.
[0094] For the sintered product of the invention, the composition
of the basic constituent components, indium oxide, tin oxide and
zinc oxide, may be indium oxide alone, or a mixture of indium oxide
and a small amount of zinc oxide, or a mixture of indium oxide, a
small amount of zinc oxide and a small amount of tin oxide, as in
the above.
[0095] Regarding the blend ratio of the constituent components, if
the atomic ratio of indium oxide is smaller than 0.80, the surface
resistance of the transparent electroconductive film to be obtained
herein will be high and the heat resistance thereof will be low. If
the atomic ratio of zinc oxide is smaller than 0.05, the
transparent electroconductive film could not be etched
satisfactorily. In this case, a small amount of water or hydrogen
may be added to the system where the sintered product is sputtered
to form films, whereby the etchability of the films formed could be
improved. If the atomic ratio of zinc oxide is larger than 0.20,
the electroconductivity of the transparent electroconductive film
will be low. If the atomic ratio of tin oxide is smaller than 0.02,
the electroconductivity of targets of the sintered product will be
low; but if larger than 0.20, the surface resistance of the
transparent electroconductive film formed will be high.
[0096] The sintered product comprises the basic constituent
component, indium oxide alone, or indium oxide and zinc oxide
and/or tin oxide, and contains from 0.5 to 10 atomic %, relative to
the total of all metal atoms therein, an additional metal oxide
selected from ruthenium oxide, molybdenum oxide and vanadium oxide.
If the additional metal oxide content is smaller than 0.5 atomic %,
the work function of the transparent electroconductive film to be
obtained herein could not be increased to a satisfactory level; but
if larger than 10 atomic %, the transparency of the film will be
low. More preferably, the additional metal oxide content falls
between 1 and 7 atomic %, even more preferably between 1 and 5
atomic %, relative to the total of all metal atoms in the
composition.
[0097] The transparent electroconductive film from the sintered
product that comprises the basic components of indium oxide and
others and contains at least one additional component of ruthenium
oxide, molybdenum oxide and vanadium oxide could have an increased
work function of, for example, at least 5.45 electron volts when
the proportion of the additional components falls within the
defined range. The work function of the transparent
electroconductive film is nearly on the same level as the average
ionization potential, 5.5 to 5.6 electron volts, of organic
compounds for light-emitting substances or hole-transporting
substances for organic electroluminescent devices. Accordingly,
when the transparent electroconductive film is used as the anode in
an organic electroluminescent device, the energy gap in hole
injection from the anode to the hole transportation layer or to the
light-emitting layer in the device could be reduced, and therefore
the device could ensure increased hole injection efficiency. As a
result, the driving voltage for the organic electroluminescent
device could be lowered, heat generation that may be caused by the
energy gap between the constituent layers could be retarded in the
device, and the device could ensure long-term stable light
emission.
[0098] For producing the sintered product of the invention, for
example, employed is a method comprising blending powders of the
starting metal oxides in a predetermined ratio, uniformly mixing
and grinding the blend in a mixing and grinding machine, for
example, in a wet ball or bead mill or ultrasonically, then
granulating the resulting mixture, shaping the resulting granules
into bodies of desired form by pressing, and finally baking them
into sintered products. In this, the raw material powders are
preferably mixed and ground as fine as possible, but, in general,
they are mixed and ground to have a mean grain size of not larger
than 1 .mu.m. In the baking step, the shaped bodies are baked
generally at a temperature falling between 1,200 and 1,500.degree.
C., but preferably between 1,250 and 1,480.degree. C., for a period
of time generally falling between 10 and 72 hours, but preferably
between 24 and 48 hours. In this, the heating rate may fall between
1 and 50.degree. C./min.
[0099] [III] Third Aspect of the Invention:
[0100] The transparent electroconductive material of the invention
is of a composition that comprises one or more metal oxides
selected from indium oxide, zinc oxide and tin oxide and contains
from 0.5 to 20 atomic %, relative to the total of all metal atoms
therein, of one or more metal oxides selected from iridium oxide,
rhenium oxide and palladium oxide.
[0101] The transparent electroconductive material with better
electroconductivity is of a composition that comprises metal
oxide(s) of indium oxide, zinc oxide and tin oxide in the following
atomic ratios:
In/(In+Zn+Sn)=0.00 to 1.00,
Zn/(In+Zn+Sn)=0.00 to 0.25,
Sn/(In+Zn+Sn)=0.00 to 1.00,
[0102] and contains from 0.5 to 20 atomic %, relative to the total
of all metal atoms therein, of one or more metal oxides selected
from iridium oxide, rhenium oxide and palladium oxide.
[0103] More preferably, the transparent electroconductive material
is of a composition that comprises metal oxides of indium oxide,
zinc oxide and tin oxide in the following atomic ratios:
In/(In+Zn+Sn)=0.50 to 1.00,
Zn/(In+Zn+Sn)=0.05 to 0.25,
Sn/(In+Zn+Sn)=0.00 to 0.50,
[0104] and contains from 0.5 to 20 atomic %, relative to the total
of all metal atoms therein, of one or more metal oxides selected
from iridium oxide, rhenium oxide and palladium oxide.
[0105] The transparent electroconductive material with much better
electroconductivity is of a composition that comprises metal oxides
of indium oxide, zinc oxide and tin oxide in the following atomic
ratios:
In/(In+Zn+Sn)=0.75 to 0.95,
Zn/(In+Zn+Sn)=0.05 to 0.20,
Sn/(In+Zn+Sn)=0.00 to 0.20,
[0106] and contains from 0.5 to 20 atomic %, relative to the total
of all metal atoms therein, of one or more metal oxides selected
from iridium oxide, rhenium oxide and palladium oxide.
[0107] Most preferably, the transparent electroconductive material
is of a composition that comprises metal oxides of indium oxide,
zinc oxide and tin oxide in the following atomic ratios:
In/(In+Zn+Sn)=0.85 to 0.95,
Zn/(In+Zn+Sn)=0.07 to 0.20,
Sn/(In+Zn+Sn)=0.00 to 0.15,
[0108] and contains from 0.5 to 20 atomic %, relative to the total
of all metal atoms therein, of one or more metal oxides selected
from iridium oxide, rhenium oxide and palladium oxide.
[0109] For the transparent electroconductive material of the
invention, the composition of the basic constituent components,
indium oxide, zinc oxide and tin oxide, or a mixture of these metal
oxides may be indium oxide, zinc oxide or tin oxide each alone, or
a mixture of indium oxide and zinc oxide, or a mixture of indium
oxide and tin oxide, or a mixture of indium oxide, zinc oxide and
tin oxide, as in the above.
[0110] Regarding the blend ratio of the constituent components,
indium oxide is not always needed herein. However, in order that
the material could be formed into transparent electroconductive
films with low surface resistance, it is desirable the atomic ratio
of indium oxide is at least 0.5. Zinc oxide is not always needed
herein. However, in order that the material could be formed into
transparent electroconductive films with improved etchability, a
small amount of zinc oxide is added to the composition for the
material. For this, for example, the atomic ratio of zinc oxide may
be at least 0.05. If the etchability of the transparent
electroconductive films formed from the material is poor, a small
amount of water or hydrogen may be added to the system where the
sintered product of the material is sputtered to form the films,
whereby the etchability of the films formed could be improved. If
the atomic ratio of zinc oxide is larger than 0.25, the durability
of the transparent electroconductive films will be low. Tin oxide
is not always needed herein, but is preferably present in the
material of the invention in order that targets formed from the
material are desired to have high electroconductivity. However,
when the transparent electroconductive films to be formed from the
targets are desired to have low surface resistance, it is
preferable that the atomic ratio of tin oxide is at most 0.5 in the
material.
[0111] In the material, the basic constituent components shall be
combined with any one of iridium oxide, rhenium oxide and palladium
oxide or with a mixture of the metal oxides that may be in any
desired ratio. The proportion of the additional metal oxides to be
in the material shall fall between 0.5 and 20 atomic % relative to
the total of all metal atoms constituting the material that
includes the additional metal oxides. It may be given by the
following formulae, in terms of the atomic ratio of the metals:
Ir/(In+Zn+Sn+Ir)=0.005 to 0.20,
Re/(In+Zn+Sn+Re)=0.005 to 0.20,
Pd/(In+Zn+Sn+Pd)=0.005 to 0.20,
[0112] preferably,
Ir/(In+Zn+Sn+Ir)=0.01 to 0.10,
Re/(In+Zn+Sn+Re)=0.01 to 0.10,
Pd/(In+Zn+Sn+Pd)=0.01 to 0.10,
[0113] more preferably,
Ir/(In+Zn+Sn+Ir)=0.03 to 0.08,
Re/(In+Zn+Sn+Re)=0.03 to 0.08,
Pd/(In+Zn+Sn+Pd)=0.03 to 0.08.
[0114] If the proportion of the additional components of iridium
oxide, rhenium oxide and palladium oxide is smaller than 0.5 atomic
%, the work function of the transparent electroconductive film to
be obtained herein could not be increased to a satisfactory level;
but if larger than 20 atomic %, the transparency of the film will
be low.
[0115] The metal oxide composition comprising the basic constituent
components as above and containing from 0.5 to 20 atomic %,
relative to the total of all metal atoms therein, of iridium oxide,
rhenium oxide and palladium oxide may be sintered to give
sputtering targets, and the targets give transparent
electroconductive films through sputtering. The films could have a
light transmittance of at least 70%, and a work function of at
least 5.4 electron volts. The work function of the films is nearly
on the same level as the average ionization potential, 5.5 to 5.6
electron volts, of organic compounds for light-emitting substances
or hole-transporting substances for organic electroluminescent
devices. Accordingly, when the transparent electroconductive film
is used as the anode in an organic electroluminescent device, the
energy gap in hole injection from the anode to the hole
transportation layer or to the light-emitting layer in the device
could be reduced, and therefore the device could ensure increased
hole injection efficiency. As a result, the driving voltage for the
organic electroluminescent device could be lowered, heat generation
that may be caused by the energy gap between the constituent layers
could be retarded in the device, and the device could ensure
long-term stable light emission.
[0116] For producing the transparent electroconductive material of
the invention, for example, employed is a method comprising
blending powders of the starting metal oxides in a predetermined
ratio, followed by uniformly mixing and grinding the resulting
blend in a mixing and grinding machine, for example, in a wet ball
or bead mill or ultrasonically. In this, the raw material powders
are preferably mixed and ground as fine as possible, but, in
general, they are mixed and ground to have a mean grain size of not
larger than 1 .mu.m.
[0117] To obtain sintered products from the transparent
electroconductive material, for example, the material is
granulated, then the resulting granules are shaped into bodies of
desired form by pressing, and the shaped bodies are finally baked.
In the baking step, the shaped bodies are baked generally at a
temperature falling between 1,200 and 1,500.degree. C., but
preferably between 1,250 and 1,480.degree. C., for a period of time
generally falling between 10 and 72 hours, but preferably between
24 and 48 hours. In this, the heating rate may fall between 1 and
50.degree. C./min.
[0118] [IV] Fourth Aspect of the Invention:
[0119] The transparent electroconductive material of the invention
is of a composition that comprises metal oxide(s) of tin oxide,
indium oxide and zinc oxide in the following atomic ratios:
Sn/(Sn+In+Zn)=0.55 to 1.00,
In/(Sn+In+Zn)=0.00 to 0.45,
Zn/(Sn+In+Zn)=0.00 to 0.25,
[0120] and contains from 0.5 to 10 atomic %, relative to the total
of all metal atoms therein, of one or more metal oxides selected
from vanadium oxide, molybdenum oxide and ruthenium oxide.
[0121] More preferably, the transparent electroconductive material
is of a composition that comprises metal oxides of tin oxide,
indium oxide and zinc oxide in the following atomic ratios:
Sn/(Sn+In+Zn)=0.60 to 0.95,
In/(Sn+In+Zn)=0.00 to 0.35,
Zn/(Sn+In+Zn)=0.05 to 0.20,
[0122] and contains from 0.5 to 10 atomic %, relative to the total
of all metal atoms therein, of one or more metal oxides selected
from vanadium oxide, molybdenum oxide and ruthenium oxide.
[0123] Even more preferably, the transparent electroconductive
material is of a composition that comprises metal oxides of tin
oxide, indium oxide and zinc oxide in the following atomic
ratios:
Sn/(Sn+In+Zn)=0.55 to 0.95,
In/(Sn+In+Zn)=0.00 to 0.40,
Zn/(Sn+In+Zn)=0.05 to 0.25,
[0124] and contains from 0.5 to 10 atomic %, relative to the total
of all metal atoms therein, of one or more metal oxides selected
from vanadium oxide, molybdenum oxide and ruthenium oxide.
[0125] Still more preferably, the transparent electroconductive
material is of a composition that comprises metal oxides of tin
oxide, indium oxide and zinc oxide in the following atomic
ratios:
Sn/(Sn+In+Zn)=0.55 to 0.95,
In/(Sn+In+Zn)=0.00 to 0.40,
Zn/(Sn+In+Zn)=0.05 to 0.20,
[0126] and contains from 0.5 to 10 atomic %, relative to the total
of all metal atoms therein, of one or more metal oxides selected
from vanadium oxide, molybdenum oxide and ruthenium oxide.
[0127] Most preferably, the transparent electroconductive material
is of a composition that comprises metal oxides of tin oxide,
indium oxide and zinc oxide in the following atomic ratios:
Sn/(Sn+In+Zn)=0.60 to 0.95,
In/(Sn+In+Zn)=0.00 to 0.35,
Zn/(Sn+In+Zn)=0.05 to 0.20,
[0128] and contains from 0.5 to 10 atomic %, relative to the total
of all metal atoms therein, of one or more metal oxides selected
from vanadium oxide, molybdenum oxide and ruthenium oxide.
[0129] For the transparent electroconductive material of the
invention, the composition of the basic constituent components, tin
oxide, indium oxide and zinc oxide, or a mixture of these metal
oxides may be tin oxide, indium oxide or zinc oxide each alone, or
a mixture of tin oxide and indium oxide, or a mixture of tin oxide
and zinc oxide, or a mixture of tin oxide, indium oxide and zinc
oxide, as in the above.
[0130] Regarding the blend ratio of the basic constituent
components, it is desirable that the atomic ratio of tin oxide is
at least 0.55 in order that the cost of the material could be
reduced and that the material could be formed into transparent
electroconductive films with good heat resistance. Indium oxide is
not always needed herein. However, in order that the material could
be formed into transparent electroconductive films with high
electroconductivity, it is desirable the atomic ratio of indium
oxide is at most 0.45. If the atomic ratio of indium oxide is
larger than 0.45, the costs for producing transparent
electroconductive films from the material will increase. Zinc oxide
is not always needed herein. However, in order that the material
could be formed into transparent electroconductive films with
improved etchability, zinc oxide may be added to the composition
for the material. The atomic ratio of zinc oxide to be added to the
composition is preferably at least 0.05. In order to improve the
wet heat resistance of the transparent electroconductive films
formed from the material, the atomic ratio of zinc oxide to be in
the material is preferably at most 0.25. If the etchability of the
transparent electroconductive films formed from the material is
poor, a small amount of water or hydrogen may be added to the
system where the sintered product of the material is sputtered to
form the films, whereby the etchability of the films formed could
be improved.
[0131] In the material, the basic constituent components shall be
combined with any one of vanadium oxide, molybdenum oxide and
ruthenium oxide or with a mixture of the metal oxides that may be
in any desired ratio. The proportion of the additional metal oxides
to be in the material shall fall between 0.5 and 10 atomic %
relative to the total of all metal atoms constituting the material
that includes the additional metal oxides. It may be given by the
following formulae, in terms of the atomic ratio of the metals:
V/(In+Zn+Sn+V)=0.005 to 0.10,
Mo/(In+Zn+Sn+Mo)=0.005 to 0.10,
Ru/(In+Zn+Sn+Ru)=0.005 to 0.10,
[0132] preferably,
V/(In+Zn+Sn+V)=0.01 to 0.08,
Mo/(In+Zn+Sn+Mo)=0.01 to 0.08,
Ru/(In+Zn+Sn+Ru)=0.01 to 0.08,
[0133] more preferably,
V/(In+Zn+Sn+V)=0.02 to 0.05,
Mo/(In+Zn+Sn+Mo)=0.02 to 0.05,
Ru/(In+Zn+Sn+Ru)=0.02 to 0.05.
[0134] If the proportion of the additional component of any of
vanadium oxide, molybdenum oxide or ruthenium oxide or their
mixture is smaller than 0.5 atomic %, the work function of the
transparent electroconductive film to be obtained herein could not
be increased to a satisfactory level; but if larger than 10 atomic
%, the transparency of the film will be low.
[0135] The metal oxide composition comprising the basic constituent
components as above and containing from 0.5 to 10 atomic %,
relative to the total of all metal atoms therein, of vanadium
oxide, molybdenum oxide or ruthenium oxide may be sintered to give
sputtering targets, and the targets give transparent
electroconductive films through sputtering. The films could have a
light transmittance of at least 70%, and a work function of at
least 5.4 electron volts. The work function of the films is nearly
on the same level as the average ionization potential, 5.5 to 5.6
electron volts, of organic compounds for light-emitting substances
or hole-transporting substances for organic electroluminescent
devices. Accordingly, when the transparent electroconductive film
is used as the anode in an organic electroluminescent device, the
energy gap in hole injection from the anode to the hole
transportation layer or to the light-emitting layer in the device
could be reduced, and therefore the device could ensure increased
hole injection efficiency. As a result, the driving voltage for the
organic electroluminescent device could be lowered, heat generation
that may be caused by the energy gap between the constituent layers
could be retarded in the device, and the device could ensure
long-term stable light emission.
[0136] For producing the transparent electroconductive material of
the invention, for example, employed is a method comprising
blending powders of the starting metal oxides in a predetermined
ratio, followed by uniformly mixing and grinding the resulting
blend in a mixing and grinding machine, for example, in a wet ball
or bead mill or ultrasonically. In this, the raw material powders
are preferably mixed and ground as fine as possible, but, in
general, they are mixed and ground to have a mean grain size of not
larger than 1 .mu.m.
[0137] To obtain sintered products from the transparent
electroconductive material, for example, the material is
granulated, then the resulting granules are shaped into bodies of
desired form by pressing, and the shaped bodies are finally baked.
In the baking step, the shaped bodies are baked generally at a
temperature falling between 1,200 and 1,500.degree. C., but
preferably between 1,250 and 1,480.degree. C., for a period of time
generally falling between 10 and 72 hours, but preferably between
24 and 48 hours. In this, the heating rate may fall between 1 and
50.degree. C./min. The sintered products formed under the condition
could have a specific resistance of at most 10
m.OMEGA..multidot.cm.
[0138] The sintered products thus obtained are machined into bodies
fittable to sputtering units, and a fitting tool is attached to
each body. In that manner, obtained are sputtering targets with
good electroconductivity that could be sputtered stably.
[0139] [V] Transparent Electroconductive Glass and Films of the
First to Fourth Aspects of the Invention:
[0140] The targets produced in the manner mentioned above may be
sputtered to form films on transparent substrates. The transparent
substrates may be any conventional one, including glass substrates,
and synthetic resin films and sheets with high transparency.
Preferred synthetic resins for the films and sheets are
polycarbonate resins, polymethyl methacrylate resins, polyester
resins, polyether-sulfone resins, polyarylate resins, etc.
[0141] For sputtering the targets to form transparent
electroconductive films on transparent substrates, preferably used
are magnetron sputtering units. The sputtering condition in the
unit where the films are formed is described. The plasma output may
vary, depending on the surface area of the target used and on the
thickness of the transparent electroconductive film to be formed,
but, in general, it may fall between 0.3 and 4 W per cm.sup.2 of
the surface area of the target, and the period of time for which
the target is sputtered to form the film may fall between 5 and 120
minutes. Under the condition, the transparent electroconductive
films formed could have a desired thickness. The thickness of the
transparent electroconductive films shall vary, depending on the
type the display devices in which they are sued, but, in general,
it may fall between 200 and 6000 angstroms, preferably between 300
and 2000 angstroms.
[0142] The targets of the sintered products may also be used for
forming films in electron-beaming units or ion-plating units. In
these units, the targets could be formed into transparent
electroconductive films under the same condition as above.
[0143] In the transparent electroconductive glass and films of the
invention thus produced in the manner as above, the transparent
electroconductive layer formed on a transparent substrate has high
light transmittance and low specific resistance. The transparent
electroconductive layer is well etched to give a transparent
electrode. Specifically, after it is etched with hydrochloric acid
or oxalic acid, its cross section in the boundary between the
etched part and the non-etched part has a smooth profile, and the
etched part is clearly differentiated from the non-etched part. The
etched layer forms an electrode line circuit having a uniform width
and a uniform thickness. Accordingly, the transparent
electroconductive layer in the transparent electroconductive glass
and films of the invention can be well etched in any ordinary
manner to give good transparent electrodes. When a transparent
electroconductive film with poor processability into electrodes is
etched to form an electrode, the electric resistance of the circuit
that comprises the resulting electrode will partly increase or
decrease, and, as the case may be, the insulating area in the
circuit will fail to prevent electric conduction and the circuit
will break down. Contrary to this, the circuit that comprises the
transparent electrode fabricated in the invention is free from the
troubles.
[0144] In the first aspect of the invention, the transparent
electroconductive layer formed from the sintered product that
comprises the three-component metal oxides and containing an oxide
of a positive tetra-valent or higher poly-valent metal has a high
light transmittance of at least 75% and are therefore highly
transparent. In addition, It has a specific resistance of at most 5
m.OMEGA..multidot.cm and a work function of at least 5.45. With the
layer, the transparent electroconductive glass and films of the
invention are favorable to transparent electrodes for organic
electroluminescent devices. In this embodiment, if the proportion
of the additional metal oxide with a positive tetra-valent or
higher poly-valent metal is too large, the electroconductivity of
the layer will be low. Therefore, when the layer is desired to have
high electroconductivity, it shall have a laminate structure
comprising a lower layer of the three-component metal oxides and an
upper layer of the additional metal oxide with a positive
tetra-valent or higher poly-valent metal. Thus layered, the two
shall be sintered. The two-layered, transparent electroconductive
layer could have higher electroconductivity, and its work function
could be nearly on the same level as that of organic compounds for
organic electroluminescent devices. The layer is favorably used as
an electrode in organic electroluminescent devices.
[0145] In the transparent electroconductive glass and films of the
second aspect of the invention thus produced in the manner as
above, the metal oxide composition of the transparent
electroconductive layer is the same as that of the sintered product
used for forming the layer. Regarding its transparency, the
transparent electroconductive layer has a light transmittance of
larger than 75% for light having a wavelength of 500 nm. Regarding
its electroconductivity, the layer has a specific resistance of at
most 5 m.OMEGA..multidot.cm. As mentioned hereinabove, the work
function of the layer is at least 5.45 electron volts and is higher
than that of ordinary ITO films.
[0146] In the transparent electroconductive glass and films of the
third aspect of the invention thus produced in the manner as above,
the metal oxide composition of the transparent electroconductive
layer is the same as that of the sintered product used for forming
the layer. Regarding its transparency, the transparent
electroconductive layer has a light transmittance of larger than
70% for light having a wavelength of 500 nm. Regarding its
electroconductivity, the layer generally has a specific resistance
of at most 5 m.OMEGA..multidot.cm. As mentioned hereinabove, the
work function of the layer is higher than that of ordinary ITO
films, and is at least 5.4 electron volts nearly on the same level
as the ionization potential of organic compounds for light-emitting
layers or hole transportation layers in organic electroluminescent
devices.
[0147] In the transparent electroconductive glass and films of the
fourth aspect of the invention thus produced in the manner as
above, the metal oxide composition of the transparent
electroconductive layer is the same as that of the sintered product
used for forming the layer. Regarding its transparency, the
transparent electroconductive layer has a light transmittance of
larger than 70% for light having a wavelength of 500 nm. As
mentioned hereinabove, the work function of the layer is higher
than that of ordinary ITO films, and is at least 5.4 electron volts
nearly on the same level as the ionization potential of organic
compounds for light-emitting layers or hole transportation layers
in organic electroluminescent devices.
[0148] Accordingly, the transparent electroconductive glass and
films of the invention are favorably used as transparent electrodes
in various display devices such as typically organic
electroluminescent devices.
[0149] The invention is described in more detail with reference to
the following Examples, which, however, are not intended to
restrict the scope of the invention.
[0150] First Aspect of the Invention
EXAMPLE I-1
[0151] (1) Production of Sintered Discs:
[0152] Raw material powders of indium oxide, tin oxide and zinc
oxide were fed into a wet ball mill in the following atomic
ratios:
In/(In+Sn+Zn)=0.50
Sn/(In+Sn+Zn)=0.25,
Zn/(In+Sn+Zn)=0.25,
[0153] and mixed and ground therein for 72 hours. The resulting
mixture was granulated, and then pressed into discs having a
diameter of 4 inches and a thickness of 5 mm. The discs were put
into a baking furnace and baked therein under pressure at
1400.degree. C. for 36 hours.
[0154] The sintered discs had a density of 6.6 g/cm.sup.3 and a
bulk resistance of 0.95 m.OMEGA..multidot.cm.
[0155] Through X-ray diffractiometric analysis for the
crystallinity of the sintered discs, it was verified that crystals
of indium oxide, crystals of a hexagonal phyllo-compound of indium
oxide and zinc oxide represented by In.sub.2O.sub.3.(ZnO)m with m
being 4, 5 and 7, and crystals of a spinel-structured compound of
essentially Zn.sub.2SnO.sub.4 were formed in the sintered
discs.
[0156] The data are given in Table I-1.
[0157] (2) Production of Transparent Electroconductive Glass:
[0158] The sintered product having been prepared in (1) was formed
into sputtering targets having a diameter of 4 inches and a
thickness of 5 mm. The target was set in a DC magnetron sputtering
unit, and sputtered onto a glass substrate set therein.
[0159] Regarding the sputtering condition, the atmosphere in the
unit was argon gas combined with a suitable amount of oxygen gas;
the sputtering pressure was 3.times.10.sup.-1Pa; the ultimate
vacuum degree was 5.times.10.sup.-4 Pa; the substrate temperature
was 25.degree. C.; the power applied was 100 W; the time for film
deposition was 14 minutes.
[0160] The transparent electroconductive film formed on the glass
substrate had a thickness of 1,200 angstroms, and was amorphous.
Its light transmittance for light having a wavelength of 500 nm was
measured with a spectrophotometer, and was 79%. The specific
resistance of the film, measured according to a 4-probe method, was
0.36 m.OMEGA..multidot.cm, and the electroconductivity of the film
was high. The work function of the film was measured through UV
photoelectron spectrometry.
[0161] (3) Evaluation of Processability of Transparent
Electroconductive Film:
[0162] The transparent electroconductive film formed on the glass
substrate in (2) was coated with a resist, exposed via a mask with
linear holes therethrough, and developed. With the patterned resist
thereon, the film was etched with an aqueous solution of
hydrochloric acid. In the film thus etched, the boundary between
the etched area and the non-etched area had a smooth inclined
surface. The part of the film that had been contacted with the
etching solution was removed, and no film residue remained in the
area where the film had been contacted with the etching
solution.
[0163] The evaluation data are given in Table I-2.
EXAMPLE I-2
[0164] Transparent electroconductive glass was produced in the same
manner as in Example I-1, except that the glass substrate was kept
at 215.degree. C. during the sputtering process (2).
[0165] The transparent electroconductive film formed on the glass
substrate was evaluated, and the data are given in Table I-2.
EXAMPLE I-3
[0166] A transparent electroconductive film was produced in the
same manner as in Example I-1, except that a polycarbonate
substrate having a thickness of 0.1 mm was used as the transparent
glass substrate in the step (1).
[0167] The transparent electroconductive film formed on the
polycarbonate substrate was evaluated, and the data are given in
Table I-2.
EXAMPLE I-4
[0168] (1) Production of Sintered Discs:
[0169] Sintered discs were produced in the same manner as in
Example I-1. In this, however, raw material powders of indium
oxide, tin oxide and zinc oxide were mixed in the following atomic
ratios:
In/(In+Sn+Zn)=0.50
Sn/(In+Sn+Zn)=0.45,
Zn/(In+Sn+Zn)=0.05.
[0170] The sintered discs had a density of 6.8 g/cm.sup.3 and a
bulk resistance of 0.98 m.OMEGA..multidot.cm. Regarding the
crystallinity of the sintered discs, it was verified that crystals
of indium oxide, crystals of a hexagonal phyllo-compound of indium
oxide and zinc oxide represented by In.sub.2O.sub.3.(ZnO)m with m
being 4, 5 and 7, and crystals of a spinel-structured compound of
essentially Zn.sub.2SnO.sub.4 were formed in the sintered
discs.
[0171] The data are given in Table I-1.
[0172] (2) Production of Transparent Electroconductive Glass:
[0173] Transparent electroconductive glass was produced in the same
manner as in the step (2) in Example I-1. In this, however, the
sintered discs prepared in the previous step (1) were used.
[0174] (3) Evaluation of Processability of Transparent
Electroconductive Film:
[0175] The processability of the transparent electroconductive film
formed on the glass substrate in the previous step (2) was
evaluated in the same manner as in the step (3) in Example I-1.
[0176] The evaluation data are given in Table I-2.
EXAMPLE I-5
[0177] (1) Production of Sintered Discs:
[0178] Sintered discs were produced in the same manner as in
Example I-1. In this, however, raw material powders of indium
oxide, tin oxide and zinc oxide were mixed in the following atomic
ratios:
In/(In+Sn+Zn)=0.70
Sn/(In+Sn+Zn)=0.25,
Zn/(In+Sn+Zn)=0.05.
[0179] The sintered discs had a density of 6.8 g/cm.sup.3 and a
bulk resistance of 0.87 m.OMEGA..multidot.cm. Regarding the
crystallinity of the sintered discs, it was verified that crystals
of indium oxide, crystals of a hexagonal phyllo-compound of indium
oxide and zinc oxide represented by In.sub.2O.sub.3.(ZnO)m with m
being 4, 5 and 7, and crystals of a spinel-structured compound of
essentially Zn.sub.2SnO.sub.4 were formed in the sintered
discs.
[0180] The data are given in Table I-1.
[0181] (2) Production of Transparent Electroconductive Glass:
[0182] Transparent electroconductive glass was produced in the same
manner as in the step (2) in Example I-1. In this, however, the
sintered discs prepared in the previous step (1) were used.
[0183] (3) Evaluation of Processability of Transparent
Electroconductive Film:
[0184] The processability of the transparent electroconductive film
formed on the glass substrate in the previous step (2) was
evaluated in the same manner as in the step (3) in Example I-1.
[0185] The evaluation data are given in Table I-2.
EXAMPLE I-6
[0186] (1) Production of Sintered Discs:
[0187] Sintered discs were produced in the same manner as in
Example I-1. In this, however, raw material powders of indium
oxide, tin oxide and zinc oxide were mixed in the following atomic
ratios:
In/(In+Sn+Zn)=0.60
Sn/(In+Sn+Zn)=0.30,
Zn/(In+Sn+Zn)=0.10.
[0188] The sintered discs had a density of 6.7 g/cm.sup.3 and a
bulk resistance of 0.82 m.OMEGA..multidot.cm. Regarding the
crystallinity of the sintered discs, it was verified that crystals
of indium oxide, crystals of a hexagonal phyllo-compound of indium
oxide and zinc oxide represented by In.sub.2O.sub.3.(ZnO)m with m
being 4, 5 and 7, and crystals of a spinel-structured compound of
essentially Zn.sub.2SnO.sub.4 were formed in the sintered
discs.
[0189] The data are given in Table I-1.
[0190] (2) Production of Transparent Electroconductive Glass:
[0191] Transparent electroconductive glass was produced in the same
manner as in the step (2) in Example I-1. In this, however, the
sintered discs prepared in the previous step (1) were used.
[0192] (3) Evaluation of Processability of Transparent
Electroconductive Film:
[0193] The processability of the transparent electroconductive film
formed on the glass substrate in the previous step (2) was
evaluated in the same manner as in the step (3) in Example I-1.
[0194] The evaluation data are given in Table I-2.
EXAMPLE I-7
[0195] (1) Production of Sintered Discs:
[0196] Sintered discs were produced in the same manner as in
Example I-1. In this, however, raw material powders of indium
oxide, tin oxide and zinc oxide were mixed in the following atomic
ratios:
In/(In+Sn+Zn)=0.60
Sn/(In+Sn+Zn)=0.30,
Zn/(In+Sn+Zn)=0.10,
[0197] and the resulting mixture was further mixed with powder of
ruthenium oxide in the following ratio:
Ru/(In+Sn+Zn+Ru)=0.02.
[0198] The sintered discs had a density of 6.7 g/cm.sup.3 and a
bulk resistance of 0.80 m.OMEGA..multidot.cm. Regarding the
crystallinity of the sintered discs, it was verified that crystals
of indium oxide, crystals of a hexagonal phyllo-compound of indium
oxide and zinc oxide represented by In.sub.2O.sub.3.(ZnO)m with m
being 4, 5 and 7, and crystals of a spinel-structured compound of
essentially Zn.sub.2SnO.sub.4 were formed in the sintered
discs.
[0199] The data are given in Table I-1. In Table I-1, Me in the
column of the metal oxide composition indicates Ru (the same shall
apply to Mo and others to be mentioned hereinunder).
[0200] (2) Production of Transparent Electroconductive Glass:
[0201] Transparent electroconductive glass was produced in the same
manner as in the step (2) in Example I-1. In this, however, the
sintered discs prepared in the previous step (1) were used.
[0202] (3) Evaluation of Processability of Transparent
Electroconductive Film:
[0203] The processability of the transparent electroconductive film
formed on the glass substrate in the previous step (2) was
evaluated in the same manner as in the step (3) in Example I-1.
[0204] The evaluation data are given in Table I-2.
EXAMPLE I-8
[0205] (1) Production of Sintered Discs:
[0206] Sintered discs were produced in the same manner as in
Example I-1. In this, however, raw material powders of indium
oxide, tin oxide and zinc oxide were mixed in the following atomic
ratios:
In/(In+Sn+Zn)=0.60
Sn/(In+Sn+Zn)=0.30,
Zn/(In+Sn+Zn)=0.10,
[0207] and the resulting mixture was further mixed with powder of
molybdenum oxide in the following ratio:
Mo/(In+Sn+Zn+Mo)=0.02.
[0208] The sintered discs had a density of 6.8 g/cm.sup.3 and a
bulk resistance of 0.94 m.OMEGA..multidot.cm. Regarding the
crystallinity of the sintered discs, it was verified that crystals
of indium oxide, crystals of a hexagonal phyllo-compound of indium
oxide and zinc oxide represented by In.sub.2O.sub.3.(ZnO)m with m
being 4, 5 and 7, and crystals of a spinel-structured compound of
essentially Zn.sub.2SnO.sub.4 were formed in the sintered
discs.
[0209] The data are given in Table I-1.
[0210] (2) Production of Transparent Electroconductive Glass:
[0211] Transparent electroconductive glass was produced in the same
manner as in the step (2) in Example I-1. In this, however, the
sintered discs prepared in the previous step (1) were used.
[0212] (3) Evaluation of Processability of Transparent
Electroconductive Film:
[0213] The processability of the transparent electroconductive film
formed on the glass substrate in the previous step (2) was
evaluated in the same manner as in the step (3) in Example I-1.
[0214] The evaluation data are given in Table I-2.
EXAMPLE I-9
[0215] (1) Production of Sintered Discs:
[0216] Sintered discs were produced in the same manner as in
Example I-1. In this, however, raw material powders of indium
oxide, tin oxide and zinc oxide were mixed in the following atomic
ratios:
In/(In+Sn+Zn)=0.60
Sn/(In+Sn+Zn)=0.30,
Zn/(In+Sn+Zn)=0.10,
[0217] and the resulting mixture was further mixed with powder of
vanadium oxide in the following ratio:
V/(In+Sn+Zn+V)=0.02.
[0218] The sintered discs had a density of 6.8 g/cm.sup.3 and a
bulk resistance of 0.99 m.OMEGA..multidot.cm. Regarding the
crystallinity of the sintered discs, it was verified that crystals
of indium oxide, crystals of a hexagonal phyllo-compound of indium
oxide and zinc oxide represented by In.sub.2O.sub.3.(ZnO)m with m
being 4, 5 and 7, and crystals of a spinel-structured compound of
essentially Zn.sub.2SnO.sub.4 were formed in the sintered
discs.
[0219] The data are given in Table I-1.
[0220] (2) Production of Transparent Electroconductive Glass:
[0221] Transparent electroconductive glass was produced in the same
manner as in the step (2) in Example I-1. In this, however, the
sintered discs prepared in the previous step (1) were used.
[0222] (3) Evaluation of Processability of Transparent
Electroconductive Film:
[0223] The processability of the transparent electroconductive film
formed on the glass substrate in the previous step (2) was
evaluated in the same manner as in the step (3) in Example I-1.
[0224] The evaluation data are given in Table I-2.
COMPARATIVE EXAMPLE I-1
[0225] (1) Production of Sintered Discs:
[0226] Sintered discs were produced in the same manner as in
Example I-1. In this, however, raw material powders of indium oxide
and zinc oxide were mixed in the following atomic ratios:
In/(In+Zn)=0.85
Zn/(In+Zn)=0.15.
[0227] The sintered discs had a density of 6.75 g/cm.sup.3 and a
bulk resistance of 2.74 m.OMEGA..multidot.cm. Regarding the
crystallinity of the sintered discs, it was verified that crystals
of indium oxide, and crystals of a hexagonal phyllo-compound of
indium oxide-zinc oxide were formed in the sintered discs.
[0228] The data are given in Table I-1.
[0229] (2) Production of Transparent Electroconductive Glass:
[0230] Transparent electroconductive glass was produced in the same
manner as in the step (2) in Example I-1. In this, however, the
sintered discs prepared in the previous step (1) were used.
[0231] Since the specific resistance of the sintered discs used
herein was high, the sputtering stability thereof was poor.
Therefore, it took 17 minutes to form the film having the
predetermined thickness.
[0232] (3) Evaluation of Processability of Transparent
Electroconductive Film:
[0233] The processability of the transparent electroconductive film
formed on the glass substrate in the previous step (2) was
evaluated in the same manner as in the step (3) in Example I-1.
[0234] The evaluation data are given in Table I-2.
COMPARATIVE EXAMPLE I-2
[0235] (1) Production of Sintered Discs:
[0236] Sintered discs were produced in the same manner as in
Example I-1. In this, however, raw material powders of indium oxide
and tin oxide were mixed in the following atomic ratios:
In/(In+Sn)=0.90
Sn/(In+Sn)=0.10.
[0237] The sintered discs had a density of 6.71 g/cm.sup.3 and a
bulk resistance of 0.69 m.OMEGA..multidot.cm. Regarding the
crystallinity of the sintered discs, it was verified that crystals
of indium oxide were formed in the sintered discs.
[0238] The data are given in Table I-1.
[0239] (2) Production of Transparent Electroconductive Glass:
[0240] Transparent electroconductive glass was produced in the same
manner as in the step (2) in Example I-1. In this, however, the
sintered discs prepared in the previous step (1) were used.
[0241] (3) Evaluation of Processability of Transparent
Electroconductive Film:
[0242] The processability of the transparent electroconductive film
formed on the glass substrate in the previous step (2) was
evaluated in the same manner as in the step (3) in Example I-1.
[0243] The evaluation data are given in Table I-2.
COMPARATIVE EXAMPLE I-3
[0244] Transparent electroconductive glass was produced in the same
manner as in Comparative Example I-2. In this, however, the
temperature of the glass substrate in the sputtering step was
215.degree. C.
[0245] The transparent electroconductive film formed on the glass
substrate was evaluated, and the evaluation data are given in Table
I-2.
1TABLE I-1 (1) Example I-1 I-4 I-5 I-6 In/(In + Sn + Zn) 0.50 0.50
0.70 0.60 Sn/(In + Sn + Zn) 0.25 0.45 0.25 0.30 Zn/(In + Sn + Zn)
0.25 0.05 0.05 0.10 Density of sintered discs (g/cm.sup.3) 6.6 6.8
6.8 6.7 Bulk resistance (m.OMEGA. .multidot. cm) 0.95 0.98 0.87
0.82 Crystallinity Indium oxide yes yes yes yes Hexagonal phyllo-
yes yes yes yes compound Spinel compound yes yes yes yes
[0246]
2 TABLE I-1 (2) Comparative Example Example I-7 I-8 I-9 I-1 I-2
In/(In + Sn + Zn) 0.60 0.60 0.60 0.85 0.90 Sn/(In + Sn + Zn) 0.30
0.30 0.30 -- 0.10 Zn/(In + Sn + Zn) 0.10 0.10 0.10 0.15 -- Me/(In +
Sn + Zn + Me) 0.02 0.02 0.02 -- -- Density of sintered discs
(g/cm.sup.3) 6.7 6.8 6.8 6.75 6.71 Bulk resistance (m.OMEGA.
.multidot. cm) 0.80 0.94 0.99 2.74 0.69 Crystallinity Indium oxide
yes yes yes yes yes Hexagonal phyllo- yes yes yes no no compound
Spinel compound yes yes yes no no
[0247]
3TABLE I-2 (1) Processability Specific Work into Electrodes
Resistance of Film Light Function (cross section of Example
(m.OMEGA. .multidot. cm) Transmittance (%) Crystallinity (eV)
etched film) I-1 0.36 79 amorphous 5.11 flat I-2 0.34 79 amorphous
5.12 flat I-3 0.37 78 amorphous 5.12 flat I-4 0.24 80 amorphous
5.16 flat I-5 0.27 81 amorphous 5.18 flat I-6 0.29 80 amorphous
5.15 flat I-7 1.3 79 amorphous 5.49 flat I-8 3.5 78 amorphous 5.55
flat I-9 2.4 78 amorphous 5.57 flat
[0248]
4TABLE I-2 (2) Processability Specific Work into Electrodes
Comparative Resistance of Film Light Function (cross section of
Example (m.OMEGA. .multidot. cm) Transmittance (%) Crystallinity
(eV) etched film) I-1 0.34 80 amorphous 5.18 flat I-2 0.42 80
microcrystalline 4.97 rough I-3 0.18 82 crystalline 4.95 rough
[0249] Second Aspect of the Invention
EXAMPLE II-1
[0250] (1) Production of Sintered Discs:
[0251] Raw material powders of indium oxide and ruthenium oxide
were mixed in the following atomic ratio:
Ru/(In+Ru)=0.03,
[0252] and the mixture was fed into a wet ball, and further mixed
and ground therein for 72 hours. The resulting mixture was
granulated, and then pressed into discs having a diameter of 4
inches and a thickness of 5 mm. The discs were put into a baking
furnace and baked therein under pressure at 1400.degree. C. for 36
hours.
[0253] The sintered discs had a density of 6.8 g/cm.sup.3 and a
bulk resistance of 0.80 m.OMEGA..multidot.cm.
[0254] The data are given in Table II-1.
[0255] (2) Production of Transparent Electroconductive Glass:
[0256] The sintered product having been prepared in (1) was formed
into sputtering targets having a diameter of 4 inches and a
thickness of 5 mm. The target was set in a DC magnetron sputtering
unit, and sputtered onto a glass substrate set therein.
[0257] Regarding the sputtering condition, the atmosphere in the
unit was argon gas combined with a suitable amount of oxygen gas;
the sputtering pressure was 3.times.10.sup.-1 Pa; the ultimate
vacuum degree was 5.times.10.sup.-4 Pa; the substrate temperature
was 25.degree. C.; the power applied was 100 W; the time for film
deposition was 14 minutes.
[0258] The transparent electroconductive film formed on the glass
substrate had a thickness of 1,200 angstroms, and was amorphous.
Its light transmittance for light having a wavelength of 500 nm was
measured with a spectrophotometer, and was 79%. The specific
resistance of the film, measured according to a 4-probe method, was
0.84 m.OMEGA..multidot.cm, and the electroconductivity of the film
was high. The work function of the film was measured through UV
photoelectron spectrometry, and was 5.51 electron volts.
[0259] The evaluation data of the transparent electroconductive
film are given in Table II-2.
EXAMPLE II-2
[0260] (1) Production of Sintered Discs:
[0261] Sintered discs were produced in the same manner as in the
step (1) in Example II-1. In this, however, molybdenum oxide was
used in place of ruthenium oxide, and its atomic ratio was:
Mo/(In+Mo)=0.07.
[0262] The physical properties of the sintered discs produced
herein are given in Table II-1.
[0263] (2) Production of Transparent Electroconductive Glass:
[0264] Transparent electroconductive glass was produced in the same
manner as in the step (2) in Example II-1. In this, however, the
sintered discs prepared in the previous step (1) were used. The
transparent electroconductive film formed on the glass substrate
was evaluated, and the data of its physical properties are given in
Table II-2.
EXAMPLE II-3
[0265] (1) Production of Sintered Discs:
[0266] Sintered discs were produced in the same manner as in the
step (1) in Example II-1. In this, however, vanadium oxide was used
in place of ruthenium oxide, and its atomic ratio was:
V/(In+V)=0.05.
[0267] The physical properties of the sintered discs produced
herein are given in Table II-1.
[0268] (2) Production of Transparent Electroconductive Glass:
[0269] Transparent electroconductive glass was produced in the same
manner as in the step (2) in Example II-1. In this, however, the
sintered discs prepared in the previous step (1) were used. The
transparent electroconductive film formed on the glass substrate
was evaluated, and the data of its physical properties are given in
Table II-2.
EXAMPLE II-4
[0270] (1) Production of Sintered Discs:
[0271] Sintered discs were produced in the same manner as in the
step (1) in Example II-1. In this, however, raw material powders of
indium oxide and zinc oxide were mixed in the following atomic
ratios:
In/(In+Zn)=0.83
Zn/(In+Zn)=0.17,
[0272] and the resulting mixture was further mixed with ruthenium
oxide in the following atomic ratio:
Ru/(In+Zn+Ru)=0.020.
[0273] The physical properties of the sintered discs produced
herein are given in Table II-1.
[0274] (2) Production of Transparent Electroconductive Glass:
[0275] Transparent electroconductive glass was produced in the same
manner as in the step (2) in Example II-1. In this, however, the
sintered discs prepared in the previous step (1) were used. The
transparent electroconductive film formed on the glass substrate
was evaluated, and the data of its physical properties are given in
Table II-2.
EXAMPLE II-5
[0276] (1) Production of Sintered Discs:
[0277] Sintered discs were produced in the same manner as in the
step (1) in Example II-1. In this, however, raw material powders of
indium oxide and zinc oxide were mixed in the following atomic
ratios:
In/(In+Zn)=0.85
Zn/(In+Zn)=0.15,
[0278] and the resulting mixture was further mixed with molybdenum
oxide in the following atomic ratio:
Mo/(In+Zn+Mo)=0.020.
[0279] The physical properties of the sintered discs produced
herein are given in Table II-1.
[0280] (2) Production of Transparent Electroconductive Glass:
[0281] Transparent electroconductive glass was produced in the same
manner as in the step (2) in Example II-1. In this, however, the
sintered discs prepared in the previous step (1) were used. The
transparent electroconductive film formed on the glass substrate
was evaluated, and the data of its physical properties are given in
Table II-2.
EXAMPLE II-6
[0282] (1) Production of Sintered Discs:
[0283] Sintered discs were produced in the same manner as in the
step (1) in Example II-1. In this, however, raw material powders of
indium oxide and zinc oxide were mixed in the following atomic
ratios:
In/(In+Zn)=0.85
Zn/(In+Zn)=0.15,
[0284] and the resulting mixture was further mixed with vanadium
oxide in the following atomic ratio:
V/(In+Zn+V)=0.020.
[0285] The physical properties of the sintered discs produced
herein are given in Table II-1.
[0286] (2) Production of Transparent Electroconductive Glass:
[0287] Transparent electroconductive glass was produced in the same
manner as in the step (2) in Example II-1. In this, however, the
sintered discs prepared in the previous step (1) were used. The
transparent electroconductive film formed on the glass substrate
was evaluated, and the data of its physical properties are given in
Table II-2.
EXAMPLE II-7
[0288] (1) Production of Sintered Discs:
[0289] Sintered discs were produced in the same manner as in the
step (1) in Example II-1. In this, however, raw material powders of
indium oxide and zinc oxide were mixed in the following atomic
ratios:
In/(In+Zn)=0.93
Zn/(In+Zn)=0.07,
[0290] and the resulting mixture was further mixed with ruthenium
oxide in the following atomic ratio:
Ru/(In+Zn+Ru)=0.015.
[0291] The physical properties of the sintered discs produced
herein are given in Table II-1.
[0292] (2) Production of Transparent Electroconductive Glass:
[0293] Transparent electroconductive glass was produced in the same
manner as in the step (2) in Example II-1. In this, however, the
sintered discs prepared in the previous step (1) were used. The
transparent electroconductive film formed on the glass substrate
was evaluated, and the data of its physical properties are given in
Table II-2.
EXAMPLE II-8
[0294] (1) Production of Sintered Discs:
[0295] Sintered discs were produced in the same manner as in the
step (1) in Example II-1. In this, however, raw material powders of
indium oxide and zinc oxide were mixed in the following atomic
ratios:
In/(In+Zn)=0.90
Zn/(In+Zn)=0.10,
[0296] and the resulting mixture was further mixed with molybdenum
oxide in the following atomic ratio:
Mo/(In+Zn+Mo)=0.050.
[0297] The physical properties of the sintered discs produced
herein are given in Table II-1.
[0298] (2) Production of Transparent Electroconductive Glass:
[0299] Transparent electroconductive glass was produced in the same
manner as in the step (2) in Example II-1. In this, however, the
sintered discs prepared in the previous step (1) were used. The
transparent electroconductive film formed on the glass substrate
was evaluated, and the data of its physical properties are given in
Table II-2.
EXAMPLE II-9
[0300] (1) Production of Sintered Discs:
[0301] Sintered discs were produced in the same manner as in the
step (1) in Example II-1. In this, however, raw material powders of
indium oxide and zinc oxide were mixed in the following atomic
ratios:
In/(In+Zn)=0.90
Zn/(In+Zn)=0.10,
[0302] and the resulting mixture was further mixed with vanadium
oxide in the following atomic ratio:
V/(In+Zn+V)=0.070.
[0303] The physical properties of the sintered discs produced
herein are given in Table II-1.
[0304] (2) Production of Transparent Electroconductive Glass:
[0305] Transparent electroconductive glass was produced in the same
manner as in the step (2) in Example II-1. In this, however, the
sintered discs prepared in the previous step (1) were used. The
transparent electroconductive film formed on the glass substrate
was evaluated, and the data of its physical properties are given in
Table II-2.
EXAMPLE II-10
[0306] (1) Production of Sintered Discs:
[0307] Sintered discs were produced in the same manner as in the
step (1) in Example II-1. In this, however, raw material powders of
indium oxide and tin oxide were mixed in the following atomic
ratios:
In/(In+Sn)=0.80
Sn/(In+Sn)=0.20,
[0308] and the resulting mixture was further mixed with ruthenium
oxide in the following atomic ratio:
Ru/(In+Sn+Ru)=0.030.
[0309] The physical properties of the sintered discs produced
herein are given in Table II-1.
[0310] (2) Production of Transparent Electroconductive Glass:
[0311] Transparent electroconductive glass was produced in the same
manner as in the step (2) in Example II-1. In this, however, the
sintered discs prepared in the previous step (1) were used. The
transparent electroconductive film formed on the glass substrate
was evaluated, and the data of its physical properties are given in
Table II-2.
EXAMPLE II-11
[0312] (1) Production of Sintered Discs:
[0313] Sintered discs were produced in the same manner as in the
step (1) in Example II-1. In this, however, raw material powders of
indium oxide and tin oxide were mixed in the following atomic
ratios:
In/(In+Sn)=0.80
Sn/(In+Sn)=0.20,
[0314] and the resulting mixture was further mixed with molybdenum
oxide in the following atomic ratio:
Mo/(In+Sn+Mo)=0.070.
[0315] The physical properties of the sintered discs produced
herein are given in Table II-1.
[0316] (2) Production of Transparent Electroconductive Glass:
[0317] Transparent electroconductive glass was produced in the same
manner as in the step (2) in Example II-1. In this, however, the
sintered discs prepared in the previous step (1) were used. The
transparent electroconductive film formed on the glass substrate
was evaluated, and the data of its physical properties are given in
Table II-2.
EXAMPLE II-12
[0318] (1) Production of Sintered Discs:
[0319] Sintered discs were produced in the same manner as in the
step (1) in Example II-1. In this, however, raw material powders of
indium oxide and tin oxide were mixed in the following atomic
ratios:
In/(In+Sn)=0.80
Sn/(In+Sn)=0.20,
[0320] and the resulting mixture was further mixed with vanadium
oxide in the following atomic ratio:
V/(In+Sn+V)=0.050.
[0321] The physical properties of the sintered discs produced
herein are given in Table II-1.
[0322] (2) Production of Transparent Electroconductive Glass:
[0323] Transparent electroconductive glass was produced in the same
manner as in the step (2) in Example II-1. In this, however, the
sintered discs prepared in the previous step (1) were used. The
transparent electroconductive film formed on the glass substrate
was evaluated, and the data of its physical properties are given in
Table II-2.
EXAMPLE II-13
[0324] (1) Production of Sintered Discs:
[0325] Sintered discs were produced in the same manner as in the
step (1) in Example II-1. In this, however, raw material powders of
indium oxide and tin oxide were mixed in the following atomic
ratios:
In/(In+Sn)=0.90
Sn/(In+Sn)=0.10,
[0326] and the resulting mixture was further mixed with ruthenium
oxide in the following atomic ratio:
Ru/(In+Sn+Ru)=0.021.
[0327] The physical properties of the sintered discs produced
herein are given in Table II-1.
[0328] (2) Production of Transparent Electroconductive Glass:
[0329] Transparent electroconductive glass was produced in the same
manner as in the step (2) in Example II-1. In this, however, the
sintered discs prepared in the previous step (1) were used. The
transparent electroconductive film formed on the glass substrate
was evaluated, and the data of its physical properties are given in
Table II-2.
EXAMPLE II-14
[0330] (1) Production of Sintered Discs:
[0331] Sintered discs were produced in the same manner as in the
step (1) in Example II-1. In this, however, raw material powders of
indium oxide and tin oxide were mixed in the following atomic
ratios:
In/(In+Sn)=0.90
Sn/(In+Sn)=0.10,
[0332] and the resulting mixture was further mixed with molybdenum
oxide in the following atomic ratio:
Mo/(In+Sn+Mo)=0.020.
[0333] The physical properties of the sintered discs produced
herein are given in Table II-1.
[0334] (2) Production of Transparent Electroconductive Glass:
[0335] Transparent electroconductive glass was produced in the same
manner as in the step (2) in Example II-1. In this, however, the
sintered discs prepared in the previous step (1) were used. The
transparent electroconductive film formed on the glass substrate
was evaluated, and the data of its physical properties are given in
Table II-2.
EXAMPLE II-15
[0336] (1) Production of Sintered Discs:
[0337] Sintered discs were produced in the same manner as in the
step (1) in Example II-1. In this, however, raw material powders of
indium oxide and tin oxide were mixed in the following atomic
ratios:
In/(In+Sn)=0.90
Sn/(In+Sn)=0.10,
[0338] and the resulting mixture was further mixed with vanadium
oxide in the following atomic ratio:
V/(In+Sn+V)=0.020.
[0339] The physical properties of the sintered discs produced
herein are given in Table II-1.
[0340] (2) Production of Transparent Electroconductive Glass:
[0341] Transparent electroconductive glass was produced in the same
manner as in the step (2) in Example II-1. In this, however, the
sintered discs prepared in the previous step (1) were used. The
transparent electroconductive film formed on the glass substrate
was evaluated, and the data of its physical properties are given in
Table II-2.
EXAMPLE II-16
[0342] (1) Production of Sintered Discs:
[0343] Sintered discs were produced in the same manner as in the
step (1) in Example II-1. In this, however, raw material powders of
indium oxide, zinc oxide and tin oxide were mixed in the following
atomic ratios:
In/(In+Zn+Sn)=0.80
Zn/(In+Zn+Sn)=0.10
Sn/(In+Zn+Sn)=0.10,
[0344] and the resulting mixture was further mixed with ruthenium
oxide in the following atomic ratio:
Ru/(In+Zn+Sn+Ru)=0.022.
[0345] The physical properties of the sintered discs produced
herein are given in Table II-1.
[0346] (2) Production of Transparent Electroconductive Glass:
[0347] Transparent electroconductive glass was produced in the same
manner as in the step (2) in Example II-1. In this, however, the
sintered discs prepared in the previous step (1) were used. The
transparent electroconductive film formed on the glass substrate
was evaluated, and the data of its physical properties are given in
Table II-2.
EXAMPLE II-17
[0348] (1) Production of Sintered Discs:
[0349] Sintered discs were produced in the same manner as in the
step (1) in Example II-1. In this, however, raw material powders of
indium oxide, zinc oxide and tin oxide were mixed in the following
atomic ratios:
In/(In+Zn+Sn)=0.80
Zn/(In+Zn+Sn)=0.10
Sn/(In+Zn+Sn)=0.10,
[0350] and the resulting mixture was further mixed with molybdenum
oxide in the following atomic ratio:
Mo/(In+Zn+Sn+Mo)=0.050.
[0351] The physical properties of the sintered discs produced
herein are given in Table II-1.
[0352] (2) Production of Transparent Electroconductive Glass:
[0353] Transparent electroconductive glass was produced in the same
manner as in the step (2) in Example II-1. In this, however, the
sintered discs prepared in the previous step (1) were used. The
transparent electroconductive film formed on the glass substrate
was evaluated, and the data of its physical properties are given in
Table II-2.
EXAMPLE II-18
[0354] (1) Production of Sintered Discs:
[0355] Sintered discs were produced in the same manner as in the
step (1) in Example II-1. In this, however, raw material powders of
indium oxide, zinc oxide and tin oxide were mixed in the following
atomic ratios:
In/(In+Zn+Sn)=0.80
Zn/(In+Zn+Sn)=0.10
Sn/(In+Zn+Sn)=0.10,
[0356] and the resulting mixture was further mixed with vanadium
oxide in the following atomic ratio:
V/(In+Zn+Sn+V)=0.050.
[0357] The physical properties of the sintered discs produced
herein are given in Table II-1.
[0358] (2) Production of Transparent Electroconductive Glass:
[0359] Transparent electroconductive glass was produced in the same
manner as in the step (2) in Example II-1. In this, however, the
sintered discs prepared in the previous step (1) were used. The
transparent electroconductive film formed on the glass substrate
was evaluated, and the data of its physical properties are given in
Table II-2.
EXAMPLE II-19
[0360] (1) Production of Sintered Discs:
[0361] Sintered discs were produced in the same manner as in the
step (1) in Example II-1. In this, however, raw material powders of
indium oxide, zinc oxide and tin oxide were mixed in the following
atomic ratios:
In/(In+Zn+Sn)=0.90
Zn/(In+Zn+Sn)=0.07
Sn/(In+Zn+Sn)=0.03,
[0362] and the resulting mixture was further mixed with ruthenium
oxide in the following atomic ratio:
Ru/(In+Zn+Sn+Ru)=0.025.
[0363] The physical properties of the sintered discs produced
herein are given in Table II-1.
[0364] (2) Production of Transparent Electroconductive Glass:
[0365] Transparent electroconductive glass was produced in the same
manner as in the step (2) in Example II-1. In this, however, the
sintered discs prepared in the previous step (1) were used. The
transparent electroconductive film formed on the glass substrate
was evaluated, and the data of its physical properties are given in
Table II-2.
EXAMPLE II-20
[0366] (1) Production of Sintered Discs:
[0367] Sintered discs were produced in the same manner as in the
step (1) in Example II-1. In this, however, raw material powders of
indium oxide, zinc oxide and tin oxide were mixed in the following
atomic ratios:
In/(In+Zn+Sn)=0.90
Zn/(In+Zn+Sn)=0.07
Sn/(In+Zn+Sn)=0.03,
[0368] and the resulting mixture was further mixed with molybdenum
oxide in the-following atomic ratio:
Mo/(In+Zn+Sn+Mo)=0.035.
[0369] The physical properties of the sintered discs produced
herein are given in Table II-1.
[0370] (2) Production of Transparent Electroconductive Glass:
[0371] Transparent electroconductive glass was produced in the same
manner as in the step (2) in Example II-1. In this, however, the
sintered discs prepared in the previous step (1) were used. The
transparent electroconductive film formed on the glass substrate
was evaluated, and the data of its physical properties are given in
Table II-2.
EXAMPLE II-21
[0372] (1) Production of Sintered Discs:
[0373] Sintered discs were produced in the same manner as in the
step (1) in Example II-1. In this, however, raw material powders of
indium oxide, zinc oxide and tin oxide were mixed in the following
atomic ratios:
In/(In+Zn+Sn)=0.90
Zn/(In+Zn+Sn)=0.07
Sn/(In+Zn+Sn)=0.03,
[0374] and the resulting mixture was further mixed with vanadium
oxide in the following atomic ratio:
V/(In+Zn+Sn+V)=0.035.
[0375] The physical properties of the sintered discs produced
herein are given in Table II-1.
[0376] (2) Production of Transparent Electroconductive Glass:
[0377] Transparent electroconductive glass was produced in the same
manner as in the step (2) in Example II-1. In this, however, the
sintered discs prepared in the previous step (1) were used. The
transparent electroconductive film formed on the glass substrate
was evaluated, and the data of its physical properties are given in
Table II-2.
EXAMPLE II-22
[0378] Using a sintered disc that had been prepared in the same
manner as in the step (1) in Example II-4, as the target,
transparent electroconductive glass was produced in the same manner
as in Example II-4. In this, however, the glass substrate was kept
heated at 215.degree. C. in the sputtering step (2).
[0379] The transparent electroconductive film formed on the glass
substrate was evaluated in the same manner as in the step (2) in
Example II-1, and the data are given in Table II-2.
EXAMPLE II-23
[0380] Using a sintered disc that had been prepared in the same
manner as in the step (1) in Example II-10, as the target,
transparent electroconductive glass was produced in the same manner
as in Example II-10. In this, however, the glass substrate was kept
heated at 215.degree. C. in the sputtering step (2).
[0381] The transparent electroconductive film formed on the glass
substrate was evaluated in the same manner as in the step (2) in
Example II-1, and the data are given in Table II-2.
EXAMPLE II-24
[0382] Using a sintered disc that had been prepared in the same
manner as in the step (1) in Example II-10, as the target,
transparent electroconductive glass was produced in the same manner
as in Example II-10. In this, however, 2% by weight of water was
added to the sputtering system in the step (2).
[0383] The transparent electroconductive film formed on the glass
substrate was evaluated in the same manner as in the step (2) in
Example II-1, and the data are given in Table II-2.
[0384] The transparent electroconductive film thus produced herein
was annealed at 215.degree. C. for 1 hour, and its physical
properties were measured. Before and after the annealing, there was
found no chance in the physical properties of the film.
EXAMPLE II-25
[0385] Using a sintered disc that had been prepared in the same
manner as in the step (1) in Example II-4, as the target, a
transparent electroconductive film was produced in the same manner
as in Example II-4. In this, however, a transparent polycarbonate
substrate having a thickness of 0.1 mm was used in place of the
glass substrate used in the step (2) in Example II-4.
[0386] The transparent electroconductive film formed on the
polycarbonate substrate was evaluated in the same manner as in the
step (2) in Example II-1, and the data are given in Table II-2.
COMPARATIVE EXAMPLE II-1
[0387] A transparent electroconductive film was formed on a glass
substrate in the same manner as in the step (2) in Example II-1. In
this, however, the target used was produced from a sintered product
that had been prepared in the same manner as in the step (1) in
Example II-1 except that a mixture of powders of indium oxide and
tin oxide in the following atomic ratios:
In/(In+Zn)=0.85
Zn/(In+Zn)=0.15,
[0388] was used alone without adding thereto any additional
component of ruthenium oxide or the like.
[0389] The transparent electroconductive film formed on the glass
substrate was evaluated, and the evaluation data are given in Table
II-2.
COMPARATIVE EXAMPLE II-2
[0390] Sintered discs were produced in the same manner as in the
step (1) in Example II-1, except that a mixture of powders of
indium oxide and tin oxide in the following atomic ratios:
In/(In+Zn)=0.90
Zn/(In+Zn)=0.10,
[0391] was used alone without adding thereto any additional
component of ruthenium oxide or the like. These were formed into
sputtering targets. Using the target produced herein, transparent
electroconductive glass was produced in the same manner as in the
step (2) in Example II-1. In this, however, the glass substrate was
kept heated at 215.degree. C. in the sputtering step.
[0392] The transparent electroconductive film formed on the glass
substrate was evaluated, and the evaluation data are given in Table
II-2.
5 TABLE II-1 (1) II-1 II-2 II-3 II-4 II-5 II-6 II-7 In/(In + Zn +
Sn) 1.00 1.00 1.00 0.83 0.85 0.85 0.93 Zn/(In + Zn + Sn) -- -- --
0.17 0.15 0.15 0.07 Sn/(In + Zn + Sn) -- -- -- -- -- -- -- Ru/(In +
Zn + 0.030 -- -- 0.020 -- -- 0.015 Sn + Ru) Mo/(In + Zn + -- 0.070
-- -- 0.020 -- -- Sn + Mo) V/(In + Zn + Sn + V) -- -- 0.050 -- --
0.020 -- Density of Sintered 6.81 6.78 6.76 6.81 6.90 6.70 6.75
Discs (g/cm.sup.3) Bulk Resistance 0.80 0.88 0.95 0.95 2.74 1.72
0.95 (m.OMEGA. .multidot. cm)
[0393]
6TABLE II-1 (2) Example II-8 II-9 II-10 II-11 II-12 II-13 II-14
In/(In + Zn + Sn) 0.90 0.90 0.80 0.80 0.80 0.90 0.90 Zn/(In + Zn +
Sn) 0.10 0.10 -- -- -- -- -- Sn/(In + Zn + Sn) -- -- 0.20 0.20 0.20
0.20 0.10 Ru/(In + Zn + -- -- 0.030 -- -- 0.021 -- Sn + Ru) Mo/(In
+ Zn + 0.050 -- -- 0.070 -- -- 0.020 Sn + Mo) V/(In + Zn + Sn + V)
-- 0.070 -- -- 0.050 -- -- Density of Sintered 6.85 6.68 6.72 6.76
6.56 6.81 6.85 Discs (g/cm.sup.3) Bulk Resistance 1.85 4.85 0.74
0.92 1.92 0.79 0.93 (m.OMEGA. .multidot. cm)
[0394]
7TABLE II-1 (3) Example II-15 II-16 II-17 II-18 II-19 II-20 II-21
In/(In + Zn + Sn) 0.90 0.80 0.80 0.80 0.90 0.90 0.90 Zn/(In + Zn +
Sn) -- 0.10 0.10 0.10 0.07 0.07 0.07 Sn/(In + Zn + Sn) 0.10 0.10
0.10 0.10 0.03 0.03 0.03 Ru/(In + Zn + -- 0.022 -- -- 0.025 -- --
Sn + Ru) Mo/(In + Zn + -- -- 0.050 -- -- 0.035 -- Sn + Mo) V/(In +
Zn + Sn + V) 0.020 -- -- 0.050 -- -- 0.035 Density of Sintered 6.55
6.74 6.78 6.57 6.71 6.78 6.58 Discs (g/cm.sup.3) Bulk Resistance
1.93 0.92 1.85 1.85 0.98 1.98 1.98
[0395]
8TABLE II-2 (1) Specific Light Work Resistance of Transmittance
Function Example Film (m.OMEGA. .multidot. cm) (%) Crystallinity
(eV) II-1 0.84 79 micro- 5.51 crystalline II-2 1.51 80 micro- 5.48
crystalline II-3 4.10 79 micro- 5.49 crystalline II-4 1.70 79
amorphous 5.52 II-5 2.80 76 amorphous 5.46 II-6 3.70 79 amorphous
5.47 II-7 1.20 79 amorphous 5.45 II-6 2.10 77 amorphous 5.48 II-9
3.12 80 amorphous 5.50 II-10 0.70 81 micro- 5.52 crystalline
[0396]
9TABLE II-2 (2) Specific Light Work Resistance of Transmittance
Function Example Film (m.OMEGA. .multidot. cm) (%) Crystallinity
(eV) II-11 1.47 78 micro- 5.50 crystalline II-12 3.74 80 micro-
5.48 crystalline II-13 0.71 80 micro- 5.47 crystalline II-14 1.56
76 micro- 5.46 crystalline II-15 2.65 78 micro- 5.47 crystalline
II-16 0.65 78 amorphous 5.54 II-17 2.56 74 amorphous 5.48 II-18
3.62 76 amorphous 5.49 II-19 0.72 79 amorphous 5.55 II-20 1.27 76
amorphous 5.50
[0397]
10TABLE II-2 (3) Specific Example Resistance Light Work
(Comparative of Film Transmittance Function Example) (m.OMEGA.
.multidot. cm) (%) Crystallinity (eV) II-21 4.27 75 amorphous 5.51
II-22 1.40 80 amorphous 5.53 II-23 0.71 81 crystalline 5.52 II-24
0.84 80 amorphous 5.51 II-25 1.70 78 amorphous 5.51 (II-1) 0.34 80
amorphous 5.18 (II-2) 0.18 82 crystalline 4.97
[0398] Third Aspect of the Invention
EXAMPLE III-1
[0399] (1) Production of Transparent Electroconductive
Material:
[0400] Raw material powders of indium oxide, tin oxide and iridium
oxide were fed into a wet ball mill in the following atomic
ratios:
In/(In+Zn+Sn)=0.90
Zn/(In+Zn+Sn)=0.00
Sn/(In+Zn+Sn)=0.10,
[0401] and
Ir/(In+Zn+Sn+Ir)=0.04,
[0402] and mixed and ground therein for 72 hours to prepare powder
of a transparent electroconductive material.
[0403] The atomic ratio of the metal atoms constituting the
transparent electroconductive material obtained herein is given in
Table III-1.
[0404] (2) Production of Sintered Discs:
[0405] The powdery, transparent electroconductive material obtained
in (1) was granulated, and then pressed into discs having a
diameter of 4 inches and a thickness of 5 mm. The discs were put
into a baking furnace and baked therein under pressure at
1400.degree. C. for 36 hours.
[0406] The sintered discs had a density of 6.8 g/cm.sup.3 and a
bulk resistance of 0.98 m.OMEGA..multidot.cm.
[0407] The physical properties of the sintered discs were measured,
and the data are given in Table III-1.
[0408] (3) Production of Transparent Electroconductive Glass:
[0409] The sintered product having been prepared in (2) was formed
into sputtering targets having a diameter of 4 inches and a
thickness of 5 mm. The target was set in a DC magnetron sputtering
unit, and sputtered onto a glass substrate set therein.
[0410] Regarding the sputtering condition, the atmosphere in the
unit was argon gas combined with a suitable amount of oxygen gas;
the sputtering pressure was 3.times.10.sup.-1 Pa; the ultimate
vacuum degree was 5.times.10.sup.-4 Pa; the substrate temperature
was 25.degree. C.; the power applied was 80 W; the time for film
deposition was 14 minutes.
[0411] The transparent electroconductive film formed on the glass
substrate had a thickness of 1,200 angstroms, and was amorphous.
Its light transmittance for light having a wavelength of 500 nm was
measured with a spectrophotometer, and was 81%. The specific
resistance of the film, measured according to a 4-probe method, was
1.2 m.OMEGA..multidot.cm, and the electroconductivity of the film
was high. The work function of the film was measured through V
photoelectron spectrometry, and was 5.46 electron volts.
[0412] The physical properties of the transparent electroconductive
film are given in Table III-2.
EXAMPLE III-2
[0413] (1) Production of Transparent Electroconductive Glass:
[0414] The same sputtering target as in Example III-1 was used, and
transparent electroconductive glass was produced in the same manner
as in the step (3) in Example III-1. In this, however, the
substrate temperature was 215.degree. C.
[0415] The physical properties of the transparent electroconductive
film formed on the glass substrate were measured, and the data are
given in Table III-2.
EXAMPLE III-3
[0416] (1) Production of Transparent Electroconductive
Material:
[0417] Raw material powders of indium oxide, tin oxide and iridium
oxide were fed into a wet ball mill in the following atomic
ratios:
In/(In+Zn+Sn)=0.70
Zn/(In+Zn+Sn)=0.00
Sn/(In+Zn+Sn)=0.30,
[0418] and
Ir/(In+Zn+Sn+Ir)=0.08,
[0419] and mixed and ground therein for 72 hours to prepare powder
of a transparent electroconductive material.
[0420] The atomic ratio of the metal atoms constituting the
transparent electroconductive material obtained herein is given in
Table III-1.
[0421] (2) Production of Sintered Discs:
[0422] From the powdery, transparent electroconductive material
obtained in (1), produced were sintered discs in the same manner as
in the step (2) in Example III-1.
[0423] The physical properties of the sintered discs were measured,
and the data are given in Table III-1.
[0424] (3) Production of Transparent Electroconductive Glass:
[0425] Transparent electroconductive glass was produced in the same
manner as in the step (3) in Example III-1. In this, however, used
was the sintered product that had been prepared in the previous
step (2). The physical properties of the transparent
electroconductive film formed on the glass substrate were measured,
and the data are given in Table III-2.
EXAMPLE III-4
[0426] (1) Production of Transparent Electroconductive
Material:
[0427] Raw material powders of indium oxide, tin oxide and iridium
oxide were fed into a wet ball mill in the following atomic
ratios:
In/(In+Zn+Sn)=0.25
Zn/(In+Zn+Sn)=0.00
Sn/(In+Zn+Sn)=0.75,
[0428] and
Ir/(In+Zn+Sn+Ir)=0.05,
[0429] and mixed and ground therein for 72 hours to prepare powder
of a transparent electroconductive material.
[0430] The atomic ratio of the metal atoms constituting the
transparent electroconductive material obtained herein is given in
Table III-1.
[0431] (2) Production of Sintered Discs:
[0432] From the powdery, transparent electroconductive material
obtained in (1), produced were sintered discs in the same manner as
in the step (2) in Example III-1.
[0433] The physical properties of the sintered discs were measured,
and the data are given in Table III-1.
[0434] (3) Production of Transparent Electroconductive Glass:
[0435] Transparent electroconductive glass was produced in the same
manner as in the step (3) in Example III-1. In this, however, used
was the sintered product that had been prepared in the previous
step (2). The physical properties of the transparent
electroconductive film formed on the glass substrate were measured,
and the data are given in Table III-2.
EXAMPLE III-5
[0436] (1) Production of Transparent Electroconductive
Material:
[0437] Raw material powders of indium oxide and iridium oxide were
fed into a wet ball mill in the following atomic ratios:
In/(In+Zn+Sn)=1.00
Zn/(In+Zn+Sn)=0.00
Sn/(In+Zn+Sn)=0.00,
[0438] and
Ir/(In+Zn+Sn+Ir)=0.04,
[0439] and mixed and ground therein for 72 hours to prepare powder
of a transparent electroconductive material.
[0440] The atomic ratio of the metal atoms constituting the
transparent electroconductive material obtained herein is given in
Table III-1.
[0441] (2) Production of Sintered Discs:
[0442] From the powdery, transparent electroconductive material
obtained in (1), produced were sintered discs in the same manner as
in the step (2) in Example III-1.
[0443] The physical properties of the sintered discs were measured,
and the data are given in Table III-1.
[0444] (3) Production of Transparent Electroconductive Glass:
[0445] Transparent electroconductive glass was produced in the same
manner as in the step (3) in Example III-1. In this, however, used
was the sintered product that had been prepared in the previous
step (2). The physical properties of the transparent
electroconductive film formed on the glass substrate were measured,
and the data are given in Table III-2.
EXAMPLE III-6
[0446] (1) Production of Transparent Electroconductive
Material:
[0447] Raw material powders of zinc oxide, tin oxide and iridium
oxide were fed into a wet ball mill in the following atomic
ratios:
In/(In+Zn+Sn)=0.00
Zn/(In+Zn+Sn)=0.20
Sn/(In+Zn+Sn)=0.80,
[0448] and
Ir/(In+Zn+Sn+Ir)=0.05,
[0449] and mixed and ground therein for 72 hours to prepare powder
of a transparent electroconductive material.
[0450] The atomic ratio of the metal atoms constituting the
transparent electroconductive material obtained herein is given in
Table III-1.
[0451] (2) Production of Sintered Discs:
[0452] From the powdery, transparent electroconductive material
obtained in (1), produced were sintered discs in the same manner as
in the step (2) in Example III-1.
[0453] The physical properties of the sintered discs were measured,
and the data are given in Table III-1.
[0454] (3) Production of Transparent Electroconductive Glass:
[0455] Transparent electroconductive glass was produced in the same
manner as in the step (3) in Example III-1. In this, however, used
was the sintered product that had been prepared in the previous
step (2). The physical properties of the transparent
electroconductive film formed on the glass substrate were measured,
and the data are given in Table III-2.
EXAMPLE III-7
[0456] (1) Production of Transparent Electroconductive
Material:
[0457] Raw material powders of indium oxide, zinc oxide, tin oxide
and iridium oxide were fed into a wet ball mill in the following
atomic ratios:
In/(In+Zn+Sn)=0.80
Zn/(In+Zn+Sn)=0.10
Sn/(In+Zn+Sn)=0.10,
[0458] and
Ir/(In+Zn+Sn+Ir)=0.06,
[0459] and mixed and ground therein for 72 hours to prepare powder
of a transparent electroconductive material.
[0460] The atomic ratio of the metal atoms constituting the
transparent electroconductive material obtained herein is given in
Table III-1.
[0461] (2) Production of Sintered Discs:
[0462] From the powdery, transparent electroconductive material
obtained in (1), produced were sintered discs in the same manner as
in the step (2) in Example III-1.
[0463] The physical properties of the sintered discs were measured,
and the data are given in Table III-1.
[0464] (3) Production of Transparent Electroconductive Glass:
[0465] Transparent electroconductive glass was produced in the same
manner as in the step (3) in Example III-1. In this, however, used
was the sintered product that had been prepared in the previous
step (2). The physical properties of the transparent
electroconductive film formed on the glass substrate were measured,
and the data are given in Table III-2.
EXAMPLE III-8
[0466] (1) Production of Transparent Electroconductive
Material:
[0467] Raw material powders of indium oxide, zinc oxide, tin oxide
and iridium oxide were fed into a wet ball mill in the following
atomic ratios:
In/(In+Zn+Sn)=0.05
Zn/(In+Zn+Sn)=0.90
Sn/(In+Zn+Sn)=0.05,
[0468] and
Ir/(In+Zn+Sn+Ir)=0.06,
[0469] and mixed and ground therein for 72 hours to prepare powder
of a transparent electroconductive material.
[0470] The atomic ratio of the metal atoms constituting the
transparent electroconductive material obtained herein is given in
Table III-1.
[0471] (2) Production of Sintered Discs:
[0472] From the powdery, transparent electroconductive material
obtained in (1), produced were sintered discs in the same manner as
in the step (2) in Example III-1.
[0473] The physical properties of the sintered discs were measured,
and the data are given in Table III-1.
[0474] (3) Production of Transparent Electroconductive Glass:
[0475] Transparent electroconductive glass was produced in the same
manner as in the step (3) in Example III-1. In this, however, used
was the sintered product that had been prepared in the previous
step (2). The physical properties of the transparent
electroconductive film formed on the glass substrate were measured,
and the data are given in Table III-2.
EXAMPLE III-9
[0476] (1) Production of Transparent Electroconductive
Material:
[0477] Raw material powders of indium oxide, zinc oxide and iridium
oxide were fed into a wet ball mill in the following atomic
ratios:
In/(In+Zn+Sn)=0.85
Zn/(In+Zn+Sn)=0.15
Sn/(In+Zn+Sn)=0.00,
[0478] and
Ir/(In+Zn+Sn+Ir)=0.06,
[0479] and mixed and ground therein for 72 hours to prepare powder
of a transparent electroconductive material.
[0480] The atomic ratio of the metal atoms constituting the
transparent electroconductive material obtained herein is given in
Table III-1.
[0481] (2) Production of Sintered Discs:
[0482] From the powdery, transparent electroconductive material
obtained in (1), produced were sintered discs in the same manner as
in the step (2) in Example III-1.
[0483] The physical properties of the sintered discs were measured,
and the data are given in Table III-1.
[0484] (3) Production of Transparent Electroconductive Glass:
[0485] Transparent electroconductive glass was produced in the same
manner as in the step (3) in Example III-1. In this, however, used
was the sintered product that had been prepared in the previous
step (2). The physical properties of the transparent
electroconductive film formed on the glass substrate were measured,
and the data are given in Table III-2.
EXAMPLE III-10
[0486] (1) Production of Transparent Electroconductive Glass:
[0487] The same sputtering target as in Example III-9 was used, and
transparent electroconductive glass was produced in the same manner
as in the step (3) in Example III-1. In this, however, the
substrate temperature was 215.degree. C.
[0488] The physical properties of the transparent electroconductive
film formed on the glass substrate were measured, and the data are
given in Table III-2.
EXAMPLE III-11
[0489] (1) Production of Transparent Electroconductive Film:
[0490] The same sputtering target as in Example III-10 was used,
and a transparent electroconductive film was produced in the same
manner as in the step (3) in Example III-1. In this, however, a
transparent resin film of polycarbonate was used as the substrate
in place of the glass substrate.
[0491] The physical properties of the transparent electroconductive
film formed on the resin substrate were measured, and the data are
given in Table III-2.
EXAMPLE III-12
[0492] (1) Production of Transparent Electroconductive
Material:
[0493] Raw material powders of indium oxide, tin oxide and rhenium
oxide were fed into a wet ball mill in the following atomic
ratios:
In/(In+Zn+Sn)=0.90
Zn/(In+Zn+Sn)=0.00
Sn/(In+Zn+Sn)=0.10,
[0494] and
Re/(In+Zn+Sn+Re)=0.04,
[0495] and mixed and ground therein for 72 hours to prepare powder
of a transparent electroconductive material.
[0496] The atomic ratio of the metal atoms constituting the
transparent electroconductive material obtained herein is given in
Table III-1.
[0497] (2) Production of Sintered Discs:
[0498] From the powdery, transparent electroconductive material
obtained in (1), produced were sintered discs in the same manner as
in the step (2) in Example III-1.
[0499] The physical properties of the sintered discs were measured,
and the data are given in Table III-1.
[0500] (3) Production of Transparent Electroconductive Glass:
[0501] Transparent electroconductive glass was produced in the same
manner as in the step (3) in Example III-1. In this, however, used
was the sintered product that had been prepared in the previous
step (2). The physical properties of the transparent
electroconductive film formed on the glass substrate were measured,
and the data are given in Table III-2.
EXAMPLE III-13
[0502] (1) Production of Transparent Electroconductive
Material:
[0503] Raw material powders of indium oxide, zinc oxide and rhenium
oxide were fed into a wet ball mill in the following atomic
ratios:
In/(In+Zn+Sn)=0.85
Zn/(In+Zn+Sn)=0.15
Sn/(In+Zn+Sn)=0.00
[0504] and
Re/(In+Zn+Sn+Re)=0.06,
[0505] and mixed and ground therein for 72 hours to prepare powder
of a transparent electroconductive material.
[0506] The atomic ratio of the metal atoms constituting the
transparent electroconductive material obtained herein is given in
Table III-1.
[0507] (2) Production of Sintered Discs:
[0508] From the powdery, transparent electroconductive material
obtained in (1), produced were sintered discs in the same manner as
in the step (2) in Example III-1.
[0509] The physical properties of the sintered discs were measured,
and the data are given in Table III-1.
[0510] (3) Production of Transparent Electroconductive Glass:
[0511] Transparent electroconductive glass was produced in the same
manner as in the step (3) in Example III-1. In this, however, used
was the sintered product that had been prepared in the previous
step (2). The physical properties of the transparent
electroconductive film formed on the glass substrate were measured,
and the data are given in Table III-2.
EXAMPLE III-14
[0512] (1) Production of Transparent Electroconductive Film:
[0513] The same sputtering target as in Example III-13 was used,
and a transparent electroconductive film was produced in the same
manner as in the step (3) in Example III-1. In this, however, a
transparent resin film of polycarbonate was used as the substrate
in place of the glass substrate.
[0514] The physical properties of the transparent electroconductive
film formed on the resin substrate were measured, and the data are
given in Table III-2.
EXAMPLE III-15
[0515] (1) Production of Transparent Electroconductive
Material:
[0516] Raw material powders of indium oxide, zinc oxide, tin oxide
and rhenium oxide were fed into a wet ball mill in the following
atomic ratios:
In/(In+Zn+Sn)=0.80
Zn/(In+Zn+Sn)=0.10
Sn/(In+Zn+Sn)=0.10,
[0517] and
Re/(In+Zn+Sn+Re)=0.05,
[0518] and mixed and ground therein for 72 hours to prepare powder
of a transparent electroconductive material.
[0519] The atomic ratio of the metal atoms constituting the
transparent electroconductive material obtained herein is given in
Table III-1.
[0520] (2) Production of Sintered Discs:
[0521] From the powdery, transparent electroconductive material
obtained in (1), produced were sintered discs in the same manner as
in the step (2) in Example III-1.
[0522] The physical properties of the sintered discs were measured,
and the data are given in Table III-1.
[0523] (3) Production of Transparent Electroconductive Glass:
[0524] Transparent electroconductive glass was produced in the same
manner as in the step (3) in Example III-1. In this, however, used
was the sintered product that had been prepared in the previous
step (2). The physical properties of the transparent
electroconductive film formed on the glass substrate were measured,
and the data are given in Table III-2.
EXAMPLE III-16
[0525] (1) Production of Transparent Electroconductive
Material:
[0526] Raw material powders of indium oxide, zinc oxide and
palladium oxide were fed into a wet ball mill in the following
atomic ratios:
In/(In+Zn+Sn)=0.80
Zn/(In+Zn+Sn)=0.20
Sn/(In+Zn+Sn)=0.00,
[0527] and
Pd/(In+Zn+Sn+Pd)=0.05,
[0528] and mixed and ground therein for 72 hours to prepare powder
of a transparent electroconductive material.
[0529] The atomic ratio of the metal atoms constituting the
transparent electroconductive material obtained herein is given in
Table III-1.
[0530] (2) Production of Sintered Discs:
[0531] From the powdery, transparent electroconductive material
obtained in (1), produced were sintered discs in the same manner as
in the step (2) in Example III-1.
[0532] The physical properties of the sintered discs were measured,
and the data are given in Table III-1.
[0533] (3) Production of Transparent Electroconductive Glass:
[0534] Transparent electroconductive glass was produced in the same
manner as in the step (3) in Example III-1. In this, however, used
was the sintered product that had been prepared in the previous
step (2). The physical properties of the transparent
electroconductive film formed on the glass substrate were measured,
and the data are given in Table III-2.
COMPARATIVE EXAMPLE III-1
[0535] (1) Production of Transparent Electroconductive
Material:
[0536] Raw material powders of indium oxide and zinc oxide were fed
into a wet ball mill in the following atomic ratios:
In/(In+Zn)=0.85
Zn/(In+Zn)=0.15,
[0537] and mixed and ground therein for 72 hours to prepare powder
of a transparent electroconductive material.
[0538] (2) Production of Sintered Discs:
[0539] From the transparent electroconductive material obtained in
(1), produced were sintered discs in the same manner as in the step
(2) in Example III-1.
[0540] (3) Production of Transparent Electroconductive Glass:
[0541] Transparent electroconductive glass was produced in the same
manner as in the step (3) in Example III-1. In this, however, used
was the sintered product that had been prepared in the previous
step (2). The physical properties of the transparent
electroconductive film formed on the glass substrate were measured,
and the data are given in Table III-2.
COMPARATIVE EXAMPLE III-2
[0542] (1) Production of Transparent Electroconductive
Material:
[0543] Raw material powders of indium oxide and tin oxide were fed
into a wet ball mill in the following atomic ratios:
In/(In+Sn)=0.90
Sn/(In+Sn)=0.10,
[0544] and mixed and ground therein for 72 hours to prepare powder
of a transparent electroconductive material.
[0545] (2) Production of Sintered Discs:
[0546] From the transparent electroconductive material obtained in
(1), produced were sintered discs in the same manner as in the step
(2) in Example III-1.
[0547] (3) Production of Transparent Electroconductive Glass:
[0548] Transparent electroconductive glass was produced in the same
manner as in the step (3) in Example III-1. In this, however, used
was the sintered product that had been prepared in the previous
step (2), and the glass substrate temperature was 215.degree. C.
The physical properties of the transparent electroconductive film
formed on the glass substrate were measured, and the data are given
in Table III-2.
11TABLE III-1 Example III-1 III-3 III-4 III-5 III-6 III-7 III-8
In/(In + Zn + Sn) 0.90 0.70 0.25 1.0 -- 0.80 0.05 Zn/(In + Zn + Sn)
-- -- -- -- 0.20 0.10 0.90 Sn/(In + Zn + Sn) 0.10 0.30 0.75 -- 0.80
0.10 0.05 Ir/(In + Zn + 0.04 0.08 0.05 0.04 0.05 0.06 0.06 Sn + Ir)
Re/(In + Zn + -- -- -- -- -- -- -- Sn + Re) Pd/(In + Zn + -- -- --
-- -- -- -- Sn + Pd) Density of Sintered 6.8 6.6 6.3 6.7 6.2 6.8
5.8 Discs (g/cm.sup.3) Bulk Resistance 0.98 1.4 4.7 0.92 8.9 0.95
8.9 (m.OMEGA. .multidot. cm)
[0549]
12TABLE III-1 (2) Example (Comparative Example) III-9 III-11 III-12
III-13 III-16 (III-1) (III-2) In/(In + Zn + Sn) 0.85 0.90 0.85 0.80
0.80 0.85 0.90 Zn/(In + Zn + Sn) 0.15 -- 0.15 0.10 0.20 0.15 --
Sn/(In + Zn + Sn) -- 0.10 -- 0.10 -- -- 0.10 Ir/(In + Zn + Sn + Ir)
0.06 -- -- -- -- -- -- Re/(In + Zn + Sn + Re) -- 0.04 0.06 0.05 --
-- -- Pd/(In + Zn + Sn + Pd) -- -- -- -- 0.05 -- -- Density of
Sintered Discs (g/cm.sup.3) 6.8 6.7 6.8 6.3 6.48 6.9 6.71 Bulk
Resistance (m.OMEGA. .multidot. cm) 1.0 0.85 0.94 0.73 3.4 2.4
0.69
[0550]
13TABLE III-2 (1) Substrate Specific Light Work Temperature
Resistance of Film Transmittance Function Example (.degree. C.)
(m.OMEGA. .multidot. cm) (%) Crystallinity (eV) III-1 25 1.2 81
amorphous 5.46 III-2 215 0.52 82 microcrystalline 5.45 III-3 25 1.7
82 amorphous 5.47 III-4 25 3.8 81 amorphous 5.49 III-5 25 0.80 80
amorphous 5.45 III-6 25 450 80 amorphous 5.46 III-7 25 1.1 81
amorphous 5.54 III-8 25 8.8 78 amorphous 5.48 III-9 25 1.3 82
amorphous 5.54
[0551]
14TABLE III-2 (2) Example Specific Work (Comparative Substrate
Resistance of Film Light Function Example) Temperature (.degree.
C.) (m.OMEGA. .multidot. cm) Transmittance (%) Crystallinity (eV)
III-10 215 0.56 80 amorphous 5.49 III-11 25 0.45 82 amorphous 5.45
III-12 25 0.64 81 amorphous 5.48 III-13 25 0.55 82 amorphous 5.47
III-14 25 1.3 82 amorphous 5.54 III-15 25 0.64 81 amorphous 5.48
III-16 25 360 76 amorphous 5.61 (III-1) 25 0.32 80 amorphous 5.18
(III-2) 215 0.18 82 crystalline 4.95
[0552] Fourth Aspect of the Invention
EXAMPLE IV-1
[0553] (1) Production of Raw Material Powders for Transparent
electroconductive material:
[0554] Raw material powders of tin oxide, zinc oxide and vanadium
oxide were fed into a wet ball mill in the following atomic
ratios:
Sn/(Sn+In+Zn)=0.80
In/(Sn+In+Zn)=0.00
Zn/(Sn+In+Zn)=0.20,
[0555] and
V/(Sn+In+Zn+V)=0.04,
[0556] and mixed and ground therein for 72 hours to prepare powder
of a transparent electroconductive material.
[0557] The atomic ratio of the metal atoms constituting the
transparent electroconductive material obtained herein is given in
Table IV-1.
[0558] (2) Production of Sintered Discs:
[0559] The powdery, transparent electroconductive material obtained
in (1) was granulated, and then pressed into discs having a
diameter of 4 inches and a thickness of 5 mm. The discs were put
into a baking furnace and baked therein under pressure at
1400.degree. C. for 36 hours.
[0560] The sintered discs had a density of 6.8 g/cm.sup.3 and a
bulk resistance of 6.5 m.OMEGA..multidot.cm.
[0561] The physical properties of the sintered discs were measured,
and the data are given in Table IV-1.
[0562] (3) Production of Transparent Electroconductive Glass:
[0563] The sintered product having been prepared in (1) was formed
into sputtering targets [A] having a diameter of 4 inches and a
thickness of 5 mm. The target was set in a DC magnetron sputtering
unit, and sputtered onto a glass substrate set therein.
[0564] Regarding the sputtering condition, the atmosphere in the
unit was argon gas combined with a suitable amount of oxygen gas;
the sputtering pressure was 3.times.10.sup.-1 Pa; the ultimate
vacuum degree was 5.times.10.sup.-4 Pa; the substrate temperature
was 25.degree. C.; the power applied was 100 W; the time for film
deposition was 14 minutes.
[0565] The transparent electroconductive film formed on the glass
substrate had a thickness of 1,200 angstroms, and was amorphous.
Its light transmittance for light having a wavelength of 500 nm was
measured with a spectrophotometer, and was 80%. The specific
resistance of the film, measured according to a 4-probe method, was
1,000 m.OMEGA..multidot.cm. The work function of the film was
measured through UV photoelectron spectrometry, and was 5.50
electron volts.
[0566] The physical properties of the transparent electroconductive
film are given in Table IV-2.
EXAMPLE IV-2
[0567] Using the same sputtering target [A] as in Example IV-1,
transparent electroconductive glass was produced in the same manner
as in the step (3) in Example IV-1 except for the sputtering
condition. In this, the substrate temperature was 215.degree.
C.
[0568] The physical properties of the transparent electroconductive
film formed on the glass substrate are given in Table IV-2.
EXAMPLE IV-3
[0569] (1) Production of Raw Material Powders for Transparent
Electroconductive Material:
[0570] Raw material powders for a transparent electroconductive
material were prepared in the same manner as in the step (1) in
Example IV-1, except that powders of tin oxide, zinc oxide and
vanadium oxide were mixed in the atomic ratios indicated in Table
IV-1.
[0571] (2) Production of Sintered Discs:
[0572] Sintered discs were produced in the same manner as in the
step (2) in Example IV-1, except that the powdery, transparent
electroconductive material having been prepared in the previous (1)
was used herein.
[0573] The physical properties of the sintered discs were measured,
and the data are given in Table IV-1.
[0574] (3) Production of Transparent Electroconductive Glass:
[0575] Transparent electroconductive glass was produced in the same
manner as in the step (3) in Example IV-1, except that the
sputtering target [B] of the sintered product having been prepared
in the previous (2) was used herein.
[0576] The physical properties of the transparent electroconductive
film formed herein are given in Table IV-2.
EXAMPLE IV-4
[0577] (1) Production of Raw Material Powders for Transparent
Electroconductive Material:
[0578] Raw material powders for a transparent electroconductive
material were prepared in the same manner as in the step (1) in
Example IV-1, except that powders of tin oxide, zinc oxide and
vanadium oxide were mixed in the atomic ratios indicated in Table
IV-1.
[0579] (2) Production of Sintered Discs:
[0580] Sintered discs were produced in the same manner as in the
step (2) in Example IV-1, except that the powdery, transparent
electroconductive material having been prepared in the previous (1)
was used herein.
[0581] The physical properties of the sintered discs were measured,
and the data are given in Table IV-1.
[0582] (3) Production of Transparent Electroconductive Glass:
[0583] Transparent electroconductive glass was produced in the same
manner as in the step (3) in Example IV-1, except that the
sputtering target [C] of the sintered product having been prepared
in the previous (2) was used herein.
[0584] The physical properties of the transparent electroconductive
film formed herein are given in Table IV-2.
EXAMPLE IV-5
[0585] (1) Production of Raw Material Powders for Transparent
Electroconductive Material:
[0586] Raw material powders for a transparent electroconductive
material were prepared in the same manner as in the step (1) in
Example IV-1, except that powders of tin oxide, indium oxide and
vanadium oxide were mixed in the atomic ratios indicated in Table
IV-1.
[0587] (2) Production of Sintered Discs:
[0588] Sintered discs were produced in the same manner as in the
step (2) in Example IV-1, except that the powdery, transparent
electroconductive material having been prepared in the previous (1)
was used herein.
[0589] The physical properties of the sintered discs were measured,
and the data are given in Table IV-1.
[0590] (3) Production of Transparent Electroconductive Glass:
[0591] Transparent electroconductive glass was produced in the same
manner as in the step (3) in Example IV-1, except that the
sputtering target [D] of the sintered product having been prepared
in the previous (2) was used herein.
[0592] The physical properties of the transparent electroconductive
film formed herein are given in Table IV-2.
EXAMPLE IV-6
[0593] (1) Production of Raw Material Powders for Transparent
Electroconductive Material:
[0594] Raw material powders for a transparent electroconductive
material were prepared in the same manner as in the step (1) in
Example IV-1, except that powders of tin oxide and vanadium oxide
were mixed in the atomic ratios indicated in Table IV-1.
[0595] (2) Production of Sintered Discs:
[0596] Sintered discs were produced in the same manner as in the
step (2) in Example IV-1, except that the powdery, transparent
electroconductive material having been prepared in the previous (1)
was used herein.
[0597] The physical properties of the sintered discs were measured,
and the data are given in Table IV-1.
[0598] (3) Production of Transparent Electroconductive Glass:
[0599] Transparent electroconductive glass was produced in the same
manner as in the step (3) in Example IV-1, except that the
sputtering target [E] of the sintered product having been prepared
in the previous (2) was used herein.
[0600] The physical properties of the transparent electroconductive
film formed herein are given in Table IV-2.
EXAMPLE IV-7
[0601] (1) Production of Raw Material Powders for Transparent
Electroconductive Material:
[0602] Raw material powders for a transparent electroconductive
material were prepared in the same manner as in the step (1) in
Example IV-1, except that powders of tin oxide, indium oxide, zinc
oxide and vanadium oxide were mixed in the atomic ratios indicated
in Table IV-1.
[0603] (2) Production of Sintered Discs:
[0604] Sintered discs were produced in the same manner as in the
step (2) in Example IV-1, except that the powdery, transparent
electroconductive material having been prepared in the previous (1)
was used herein.
[0605] The physical properties of the sintered discs were measured,
and the data are given in Table IV-1.
[0606] (3) Production of Transparent Electroconductive Glass:
[0607] Transparent electroconductive glass was produced in the same
manner as in the step (3) in Example IV-1, except that the
sputtering target [F] of the sintered product having been prepared
in the previous (2) was used herein.
[0608] The physical properties of the transparent electroconductive
film formed herein are given in Table IV-2.
EXAMPLE IV-8
[0609] (1) Production of Transparent Electroconductive Film:
[0610] Using a transparent polycarbonate film but not glass as the
substrate and using the sputtering target [F] that had been
prepared in Example IV-7, a transparent electroconductive film was
produced.
[0611] The physical properties of the transparent electroconductive
film formed herein are given in Table IV-2.
EXAMPLE IV-9
[0612] (1) Production of Raw Material Powders for Transparent
Electroconductive Material:
[0613] Raw material powders for a transparent electroconductive
material were prepared in the same manner as in the step (1) in
Example IV-1, except that powders of tin oxide, indium oxide, zinc
oxide and vanadium oxide were mixed in the atomic ratios indicated
in Table IV-1.
[0614] (2) Production of Sintered Discs:
[0615] Sintered discs were produced in the same manner as in the
step (2) in Example IV-1, except that the powdery, transparent
electroconductive material having been prepared in the previous (1)
was used herein.
[0616] The physical properties of the sintered discs were measured,
and the data are given in Table IV-1.
[0617] (3) Production of Transparent Electroconductive Glass:
[0618] Transparent electroconductive glass was produced in the same
manner as in the step (3) in Example IV-1, except that the
sputtering target [G] of the sintered product having been prepared
in the previous (2) was used herein.
[0619] The physical properties of the transparent electroconductive
film formed herein are given in Table IV-2.
COMPARATIVE EXAMPLE IV-1
[0620] (1) Production of Raw Material Powders for Transparent
Electroconductive Material:
[0621] Raw material powders for a transparent electroconductive
material were prepared in the same manner as in the step (1) in
Example IV-1, except that powders of indium oxide and zinc oxide
were mixed in the atomic ratios indicated in Table IV-1.
[0622] (2) Production of Sintered Discs:
[0623] Sintered discs were produced in the same manner as in the
step (2) in Example IV-1, except that the powdery, transparent
electroconductive material having been prepared in the previous (1)
was used herein.
[0624] The physical properties of the sintered discs were measured,
and the data are given in Table IV-1.
[0625] (3) Production of Transparent Electroconductive Glass:
[0626] Transparent electroconductive glass was produced in the same
manner as in the step (3) in Example IV-1, except that the
sputtering target [H] of the sintered product having been prepared
in the previous (2) was used herein.
[0627] The physical properties of the transparent electroconductive
film formed herein are given in Table IV-2.
COMPARATIVE EXAMPLE IV-2
[0628] (1) Production of Raw Material Powders for Transparent
Electroconductive Material:
[0629] Raw material powders for a transparent electroconductive
material were prepared in the same manner as in the step (1) in
Example IV-1, except that powders of tin oxide and indium oxide
were mixed in the atomic ratios indicated in Table IV-1.
[0630] (2) Production of Sintered Discs:
[0631] Sintered discs were produced in the same manner as in the
step (2) in Example IV-1, except that the powdery, transparent
electroconductive material having been prepared in the previous (1)
was used herein.
[0632] The physical properties of the sintered discs were measured,
and the data are given in Table IV-1.
[0633] (3) Production of Transparent Electroconductive Glass:
[0634] Transparent electroconductive glass was produced in the same
manner as in the step (3) in Example IV-1, except that the
sputtering target [I] of the sintered product having been prepared
in the previous (2) was used herein.
[0635] The physical properties of the transparent electroconductive
film formed herein are given in Table IV-2.
COMPARATIVE EXAMPLE IV-3
[0636] (1) Production of Transparent Electroconductive Glass:
[0637] Transparent electroconductive glass was produced in the same
manner as in the step (3) in Example IV-1. In this, however, the
sputtering target [H] that had been prepared in Comparative Example
IV-1 was used, and the temperature of the glass substrate in the
sputtering step was 215.degree. C.
[0638] The physical properties of the transparent electroconductive
film formed herein are given in Table IV-2.
COMPARATIVE EXAMPLE IV-4
[0639] (1) Production of Transparent Electroconductive Glass:
[0640] Transparent electroconductive glass was produced in the same
manner as in the step (3) in Example IV-1. In this, however, the
sputtering target [I] that had been prepared in Comparative Example
IV-2 was used, and the temperature of the glass substrate in the
sputtering step was 215.degree. C.
[0641] The physical properties of the transparent electroconductive
film formed herein are given in Table IV-2.
15TABLE IV-1 Example (Comparative Example) IV-1 IV-3 IV-4 IV-5 IV-6
IV-7 IV-9 (IV-1) (IV-2) Sn/(Sn + In + Zn) 0.80 0.95 0.55 0.80 1.00
0.80 0.80 -- 0.10 In/(Sn + In + Zn) -- -- 0.45 0.20 -- 0.10 0.15
0.85 0.90 Zn/(Sn + In + Zn) 0.20 0.05 -- -- -- 0.10 0.05 0.15 --
V/(Sn + In + Zn + V) 0.04 0.032 0.035 0.03 0.02 0.05 0.035 -- --
Density of Sintered 6.8 6.6 6.5 6.6 6.5 6.7 6.6 6.75 6.71 Discs
(g/cm.sup.3) Bulk Resistance 6.5 5.8 8.3 6.8 8.1 3.8 4.2 2.74 0.69
(m.OMEGA. .multidot. cm) Target Code [A] [B] [C] [D] [E] [F] [G]
[H] [I]
[0642]
16TABLE IV-2 Example Substrate Specific Light Work (Comparative
Target Temperature Resistance of Transmittance Function Example)
Code (.degree. C.) Film (m.OMEGA. .multidot. cm) (%) Crystallinity
(eV) IV-1 [A] 25 1000 80 amorphous 5.50 IV-2 [A] 215 1000 81
crystalline 5.51 IV-3 [B] 25 700 80 amorphous 5.49 IV-4 [C] 25 3 81
amorphous 5.48 IV-5 [D] 25 5 80 amorphous 5.47 IV-6 [E] 25 4 81
amorphous 5.46 IV-7 [F] 25 1 82 amorphous 5.48 IV-8 [F] 25 1 82
amorphous 5.48 IV-9 [G] 25 2 81 amorphous 5.48 (IV-1) [H] 25 0.34
80 amorphous 5.18 (IV-2) [I] 25 0.42 80 micro- 4.97 crystalline
(IV-3) [H] 215 0.32 80 amorphous 5.18 (IV-4) [I] 215 0.18 82
crystalline 4.95
EXAMPLE IV-10
[0643] (1) Production of Raw Material Powders for Transparent
Electroconductive Material:
[0644] Raw material powders for a transparent electroconductive
material were prepared in the same manner as in the step (1) in
Example IV-1, except that powders of tin oxide, zinc oxide and
molybdenum oxide were mixed in the atomic ratios indicated in Table
IV-3.
[0645] (2) Production of Sintered Discs:
[0646] Sintered discs were produced in the same manner as in the
step (2) in Example IV-1, except that the powdery, transparent
electroconductive material having been prepared in the previous (1)
was used herein.
[0647] The physical properties of the sintered discs were measured,
and the data are given in Table IV-3.
[0648] (3) Production of Transparent Electroconductive Glass:
[0649] Transparent electroconductive glass was produced in the same
manner as in the step (3) in Example IV-1, except that the
sputtering target [J] of the sintered product having been prepared
in the previous (2) was used herein.
[0650] The physical properties of the transparent electroconductive
film formed herein are given in Table IV-4.
EXAMPLE IV-11
[0651] (1) Production of Raw Material Powders for Transparent
Electroconductive Material:
[0652] Raw material powders for a transparent electroconductive
material were prepared in the same manner as in the step (1) in
Example IV-1, except that powders of tin oxide, zinc oxide and
molybdenum oxide were mixed in the atomic ratios indicated in Table
IV-3.
[0653] (2) Production of Sintered Discs:
[0654] Sintered discs were produced in the same manner as in the
step (2) in Example IV-1, except that the powdery, transparent
electroconductive material having been prepared in the previous (1)
was used herein.
[0655] The physical properties of the sintered discs were measured,
and the data are given in Table IV-3.
[0656] (3) Production of Transparent Electroconductive Glass:
[0657] Transparent electroconductive glass was produced in the same
manner as in the step (3) in Example IV-1, except that the
sputtering target [K] of the sintered product having been prepared
in the previous (2) was used herein.
[0658] The physical properties of the transparent electroconductive
film formed herein are given in Table IV-4.
EXAMPLE IV-12
[0659] (1) Production of Raw Material Powders for Transparent
Electroconductive Material:
[0660] Raw material powders for a transparent electroconductive
material were prepared in the same manner as in the step (1) in
Example IV-1, except that powders of tin oxide, indium oxide and
molybdenum oxide were mixed in the atomic ratios indicated in Table
IV-3.
[0661] (2) Production of Sintered Discs:
[0662] Sintered discs were produced in the same manner as in the
step (2) in Example IV-1, except that the powdery, transparent
electroconductive material having been prepared in the previous (1)
was used herein.
[0663] The physical properties of the sintered discs were measured,
and the data are given in Table IV-3.
[0664] (3) Production of Transparent Electroconductive Glass:
[0665] Transparent electroconductive glass was produced in the same
manner as in the step (3) in Example IV-1, except that the
sputtering target [L] of the sintered product having been prepared
in the previous (2) was used herein.
[0666] The physical properties of the transparent electroconductive
film formed herein are given in Table IV-4.
EXAMPLE IV-13
[0667] (1) Production of Raw Material Powders for Transparent
Electroconductive Material:
[0668] Raw material powders for a transparent electroconductive
material were prepared in the same manner as in the step (1) in
Example IV-1, except that powders of tin oxide, indium oxide, zinc
oxide and molybdenum oxide were mixed in the atomic ratios
indicated in Table IV-3.
[0669] (2) Production of Sintered Discs:
[0670] Sintered discs were produced in the same manner as in the
step (2) in Example IV-1, except that the powdery, transparent
electroconductive material having been prepared in the previous (1)
was used herein.
[0671] The physical properties of the sintered discs were measured,
and the data are given in Table IV-3.
[0672] (3) Production of Transparent Electroconductive Glass:
[0673] Transparent electroconductive glass was produced in the same
manner as in the step (3) in Example IV-1, except that the
sputtering target [M] of the sintered product having been prepared
in the previous (2) was used herein.
[0674] The physical properties of the transparent electroconductive
film formed herein are given in Table IV-4.
EXAMPLE IV-14
[0675] (1) Production of Transparent Electroconductive Glass:
[0676] Using the sputtering target [M] that had been prepared in
Example IV-13, transparent electroconductive glass was produced in
the same manner as in the step (3) in Example IV-1. In this,
however, the glass substrate temperature was 215.degree. C.
[0677] The physical properties of the transparent electroconductive
film formed herein are given in Table IV-4.
EXAMPLE IV-15
[0678] (1) Production of Transparent Electroconductive Film:
[0679] Using a transparent polycarbonate film but not glass as the
substrate and using the sputtering target [M] that had been
prepared in Example IV-13, a transparent electroconductive film was
produced in the same manner as in the step (3) in Example IV-1.
[0680] The physical properties of the transparent electroconductive
film formed herein are given in Table IV-4.
EXAMPLE IV-16
[0681] (1) Production of Raw Material Powders for Transparent
Electroconductive Material:
[0682] Raw material powders for a transparent electroconductive
material were prepared in the same manner as in the step (1) in
Example IV-1, except that powders of tin oxide, indium oxide, zinc
oxide and molybdenum oxide were mixed in the atomic ratios
indicated in Table IV-3.
[0683] (2) Production of Sintered Discs:
[0684] Sintered discs were produced in the same manner as in the
step (2) in Example IV-1, except that the powdery, transparent
electroconductive material having been prepared in the previous (1)
was used herein.
[0685] The physical properties of the sintered discs were measured,
and the data are given in Table IV-3.
[0686] (3) Production of Transparent Electroconductive Glass:
[0687] Transparent electroconductive glass was produced in the same
manner as in the step (3) in Example IV-1, except that the
sputtering target [N] of the sintered product having been prepared
in the previous (2) was used herein.
[0688] The physical properties of the transparent electroconductive
film formed herein are given in Table IV-4.
17TABLE IV-3 Example IV-10 IV-11 IV-12 IV-13 IV-16 Sn/(Sn + In +
Zn) 0.80 0.95 0.80 0.80 0.80 In/(Sn + In + Zn) -- -- 0.20 0.10 0.15
Zn/(Sn + In + Zn) 0.20 0.05 -- 0.10 0.05 Mo/(Sn + In + Zn + Mo)
0.04 0.032 0.03 0.05 0.04 Density of Sintered Discs (g/cm.sup.3)
6.7 6.5 6.7 6.8 6.7 Bulk Resistance (m.OMEGA. .multidot. cm) 5.3
4.9 5.2 3.6 3.8 Target Code [J] [K] [L] [M] [N]
[0689]
18TABLE IV-4 Substrate Specific Light Work Target Temperature
Resistance of Transmittance Function Example Code (.degree. C.)
Film (m.OMEGA. .multidot. cm) (%) Crystallinity (eV) IV-10 [J] 25
850 80 amorphous 5.47 IV-11 [K] 25 650 81 crystalline 5.49 IV-12
[L] 25 8 80 amorphous 5.49 IV-13 [M] 25 1 81 amorphous 5.48 IV-14
[M] 215 0.8 80 amorphous 5.47 IV-15 [M] 25 1 81 amorphous 5.48
IV-16 [N] 25 2 81 amorphous 5.46
EXAMPLE IV-17
[0690] (1) Production of Raw Material Powders for Transparent
Electroconductive Material:
[0691] Raw material powders for a transparent electroconductive
material were prepared in the same manner as in the step (1) in
Example IV-1, except that powders of tin oxide, zinc oxide and
ruthenium oxide were mixed in the atomic ratios indicated in Table
IV-5.
[0692] (2) Production of Sintered Discs:
[0693] Sintered discs were produced in the same manner as in the
step (2) in Example IV-1, except that the powdery, transparent
electroconductive material having been prepared in the previous (1)
was used herein.
[0694] The physical properties of the sintered discs were measured,
and the data are given in Table IV-5.
[0695] (3) Production of Transparent Electroconductive Glass:
[0696] Transparent electroconductive glass was produced in the same
manner as in the step (3) in Example IV-1, except that the
sputtering target [O] of the sintered product having been prepared
in the previous (2) was used herein.
[0697] The physical properties of the transparent electroconductive
film formed herein are given in Table IV-6.
EXAMPLE IV-18
[0698] (1) Production of Raw Material Powders for Transparent
Electroconductive Material:
[0699] Raw material powders for a transparent electroconductive
material were prepared in the same manner as in the step (1) in
Example IV-1, except that powders of tin oxide, zinc oxide and
ruthenium oxide were mixed in the atomic ratios indicated in Table
IV-5.
[0700] (2) Production of Sintered Discs:
[0701] Sintered discs were produced in the same manner as in the
step (2) in Example IV-1, except that the powdery, transparent
electroconductive material having been prepared in the previous (1)
was used herein.
[0702] The physical properties of the sintered discs were measured,
and the data are given in Table IV-5.
[0703] (3) Production of Transparent Electroconductive Glass:
[0704] Transparent electroconductive glass was produced in the same
manner as in the step (3) in Example IV-1, except that the
sputtering target [P] of the sintered product having been prepared
in the previous (2) was used herein.
[0705] The physical properties of the transparent electroconductive
film formed herein are given in Table IV-6.
EXAMPLE IV-19
[0706] (1) Production of Raw Material Powders for Transparent
Electroconductive Material:
[0707] Raw material powders for a transparent electroconductive
material were prepared in the same manner as in the step (1) in
Example IV-1, except that powders of tin oxide, indium oxide and
ruthenium oxide were mixed in the atomic ratios indicated in Table
IV-5.
[0708] (2) Production of Sintered Discs:
[0709] Sintered discs were produced in the same manner as in the
step (2) in Example IV-1, except that the powdery, transparent
electroconductive material having been prepared in the previous (1)
was used herein.
[0710] The physical properties of the sintered discs were measured,
and the data are given in Table IV-5.
[0711] (3) Production of Transparent Electroconductive Glass:
[0712] Transparent electroconductive glass was produced in the same
manner as in the step (3) in Example IV-1, except that the
sputtering target [Q] of the sintered product having been prepared
in the previous (2) was used herein.
[0713] The physical properties of the transparent electroconductive
film formed herein are given in Table IV-6.
EXAMPLE IV-20
[0714] (1) Production of Raw Material Powders for Transparent
Electroconductive Material:
[0715] Raw material powders for a transparent electroconductive
material were prepared in the same manner as in the step (1) in
Example IV-1, except that powders of tin oxide, indium oxide, zinc
oxide and ruthenium oxide were mixed in the atomic ratios indicated
in Table IV-5.
[0716] (2) Production of Sintered Discs:
[0717] Sintered discs were produced in the same manner as in the
step (2) in Example IV-1, except that the powdery, transparent
electroconductive material having been prepared in the previous (1)
was used herein.
[0718] The physical properties of the sintered discs were measured,
and the data are given in Table IV-5.
[0719] (3) Production of Transparent Electroconductive Glass:
[0720] Transparent electroconductive glass was produced in the same
manner as in the step (3) in Example IV-1, except that the
sputtering target [R] of the sintered product having been prepared
in the previous (2) was used herein.
[0721] The physical properties of the transparent electroconductive
film formed herein are given in Table IV-6.
EXAMPLE IV-21
[0722] (1) Production of Transparent Electroconductive Glass:
[0723] Using the sputtering target [RI that had been prepared in
Example IV-20, transparent electroconductive glass was produced in
the same manner as in the step (3) in Example IV-1. In this,
however, the glass substrate temperature was 215.degree. C.
[0724] The physical properties of the transparent electroconductive
film formed herein are given in Table IV-6.
EXAMPLE IV-22
[0725] (1) Production of Transparent Electroconductive Film:
[0726] Using a transparent polycarbonate film but not glass as the
substrate and using the sputtering target [R] that had been
prepared in Example IV-20, a transparent electroconductive film was
produced in the same manner as in the step (3) in Example IV-1.
[0727] The physical properties of the transparent electroconductive
film formed herein are given in Table IV-6.
EXAMPLE IV-23
[0728] (1) Production of Raw Material Powders for Transparent
Electroconductive Material:
[0729] Raw material powders for a transparent electroconductive
material were prepared in the same manner as in the step (1) in
Example IV-1, except that powders of tin oxide, indium oxide, zinc
oxide and ruthenium oxide were mixed in the atomic ratios indicated
in Table IV-5.
[0730] (2) Production of Sintered Discs:
[0731] Sintered discs were produced in the same manner as in the
step (2) in Example IV-1, except that the powdery, transparent
electroconductive material having been prepared in the previous (1)
was used herein.
[0732] The physical properties of the sintered discs were measured,
and the data are given in Table IV-5.
[0733] (3) Production of Transparent Electroconductive Glass:
[0734] Transparent electroconductive glass was produced in the same
manner as in the step (3) in Example IV-1, except that the
sputtering target [S] of the sintered product having been prepared
in the previous (2) was used herein.
[0735] The physical properties of the transparent electroconductive
film formed herein are given in Table IV-6.
19TABLE IV-5 Example IV-17 IV-18 IV-19 IV-20 IV-23 Sn/(Sn + In +
Zn) 0.80 0.95 0.80 0.80 0.80 In/(Sn + In + Zn) -- -- 0.20 0.10 0.15
Zn/(Sn + In + Zn) 0.20 0.05 -- 0.10 0.05 Ru/(Sn + In + Zn + Ru)
0.04 0.032 0.03 0.05 0.04 Density of Sintered Discs (g/cm.sup.3)
6.5 6.4 6.6 6.7 6.7 Bulk Resistance (m.OMEGA. .multidot. cm) 4.2
5.6 4.25 3.4 3.6 Target Code [O] [P] [Q] [R] [S]
[0736]
20TABLE IV-6 Substrate Specific Light Work Target Temperature
Resistance of Transmittance Function Example Code (.degree. C.)
Film (m.OMEGA. .multidot. cm) (%) Crystallinity (eV) IV-17 [O] 25
45 81 amorphous 5.51 IV-18 [P] 25 42 82 crystalline 5.48 IV-19 [Q]
25 6 81 amorphous 5.47 IV-20 [R] 25 2 80 amorphous 5.52 IV-21 [R]
215 1 82 amorphous 5.49 IV-22 [R] 25 2 80 amorphous 5.52 IV-23 [S]
25 2 81 amorphous 5.51
INDUSTRIAL APPLICABILITY
[0737] As described hereinabove, the invention provides sintered
products for transparent electroconductive films, which are formed
into films in a stable and efficient manner through sputtering or
the like, sputtering targets of the sintered products, and
transparent electroconductive glass and films formed from the
targets. The transparent electroconductive glass and films have
good transparency, good electroconductivity and good workability
into electrodes, and are therefore favorable to transparent
electrodes in organic electroluminescent devices as realizing good
hole injection efficiency therein.
* * * * *